Optically active naphthalene derivatives

ABSTRACT

The present invention is directed to optically active compounds each containing a naphthalene skeleton, and to liquid crystal compositions which contain the aforesaid optical active compounds, these compositions being suitable for ferroelectric liquid crystal devices having excellent photostability and chemical stability and having a rapid responsivity. The compounds of the present invention are represented by the general formula ##STR1## wherein X is a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a methoxy group, the latter two groups each having 1 or 2 carbon atoms; and A and B are independently represented by following formula and at least one of them contains an asymmetric carbon atom ##STR2## wherein C and D rings are independent and each of them is a 1,4-phenylene, 2,6-naphthylene, pyrimidine-2,5-diyl, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl, trans-1,3-oxathian-2,5-diyl, trans-1,3-dithian-2, 5-diyl or 1,3,2-dioxaborinane-2,5-diyl group; each of m and n is an integer of 0, 1 or 2; each of Z 1 , Z 2 , Z 3  and Z 4  is a bonding group of one or more selected from the group consisting of a single bond, --C(O)--, --O--, --CH 2  --, --CH═N--, --N═CH--, --CH═CH--, --C.tbd.C--, --N═N-- and --N(O)═N--; and Y is a hydrogen atom, a halogen atom, a cyano group, a straight-chain or branched alkyl group or an alkenylalkyl group, the latter two groups each having 1 to 20 carbon atoms.

This application is a division of application Ser. No. 137,263 filedDec. 23, 1987, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel optically active compounds eachcontaining a naphthalene skeleton and to liquid crystal compositionscontaining these compounds.

2. Description of the Prior Art

Presently, various kinds of liquid crystal display devices are used inmany fields because the display operation of these elements isadvantageously possible at a low voltage, in a low consumption ofelectric power and in a thin form and because they are photoreceptiveand therefore conveniently they do not cause eyes of operators to gettired.

Above all, TN (twisted nematic) type display systems each employing anematic liquid crystal are utilized in an extensive range. However,these display systems have the drawback that a response speed is low.

The advancement of the recent industrial technology strongly requires arapid responsivity even in the field of the liquid crystal devices, andin reply to such a requirement, many attemps have been made by improvingmaterials for the liquid crystals. As one example which can meet theabove-mentioned demand, a display device has been already suggested inwhich a photoswitching phenomenon of a ferroelectric liquid crystal isutilized [Appl. Phys. Lett., 36, 899 (1980)]. As a liquid crystal phasefor the ferroelectric liquid crystal, a chiral smectic C (SC*) phase ispractically desirable, and some of the liquid crystal compounds showingthe chiral smectic C phase have been heretofore investigated. Typicalexamples of these liquid crystal compounds are set forth in Table 1.

With regard to the ferroelectric liquid crystal compounds each having anaphthalene skeleton, Japanese Patent Laid-Open Publication No.248,790/1985 suggests the possibility of the presence of their compoundsbut does not refer to concrete examples of such compounds. In thistechnical field, it cannot be presumed at all at present what skeletonin the compound causes the ferroelectric properties in the liquidcrystal and what physical properties the ferroelectric liquid crystalhas. The inventors of the present application have found that liquidcrystal compounds each having the naphthalene skeleton show remarkablyexcellent characteristics to compounds exemplified in the aforesaidpatent publication, and the present invention has been completed on thebasis of the found knowledge.

The conventional compounds in Table 1 may isomerize in a short period oftime by light and may hydrolyze due to existent water, so that they cometo have no liquid crystal phase any more at times. The compounds havingsuch unstable factors are practically unpreferable as materials forvarious optical elements of displays and the like.

                                      TABLE 1                                     __________________________________________________________________________    Chemical Structure               Phase Transition                             __________________________________________________________________________     ##STR3##                                                                                                       ##STR4##                                     ##STR5##                                                                                                       ##STR6##                                     ##STR7##                                                                                                       ##STR8##                                    __________________________________________________________________________     The compounds 1 and 2 above are described in J. Physique, 37, C3129           (1976).                                                                       The compound 3 is described in Mol. Cryst. Liq. Cryst. Letters, 82, 61        (1982).                                                                  

SUMMARY OF THE INVENTION

An object of the present invention is to provide compounds which areuseful as novel ferroelectric liquid crystal materials or constitutionalcomponents of liquid crystal compositions having an excellentphotostability and chemical stability.

Further, another object of the present invention is to provide liquidcrystal compositions which are suitable for liquid crystal deviceshaving a rapid responsivity.

The present invention is directed to optically active naphthalenederivatives represented by the general formula (I) and liquid crystalcompositions each containing at least one of these derivatives: ##STR9##wherein X is a hydrogen atom, a halogen atom, a cyano group, an alkylgroup or methoxy group, latter two groups each having 1 or 2 carbonatoms; and A and B are independently represented by following formulaand at least one of them contains an asymmetric carbon atom ##STR10##wherein C and D rings are independent and each of them is a1,4-phenylene, 2,6-naphthylene, pyrimidine-2,5-diyl,trans-1,4-cyclohexylene, trans-1,3-dioxan-2,5-diyl,trans-1,3-oxathian-2,5-diyl, trans-1,3-dithian-2,5-diyl or1,3,2-dioxaborinane-2,5-diyl group, these groups may be monosubstitutedor multisubstituted by X; each of m and n is an integer of 0, 1 or 2;each of Z₁, Z₂, Z₃ and Z₄ is a bonding group of one or more selectedfrom the group consisting of a single bond, --C(O)--, --O--, --CH₂ --,--CH═N--, --N═CH--, --CH═CH--, --C.tbd.C--, --N═N-- and --N(O).N--; andY is a hydrogen atom, a halogen atom, a cyano group, a straight-chain orbranched alkyl group or an alkenylalkyl group latter two groups eachhaving 1 to 20 carbon atoms n which in its alkyl portion, one CH₂ groupor two unadjacent CH₂ groups may be replaced with --O--, --C(O)--,--O--C(O)-- or --C(O)--O-- and one hydrogen atom may be replaced with ahalogen atom, a cyano group or an alkoxyl group.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In order to solve the above-mentioned problems, the inventors of thepresent application have snythesized and investigated many liquidcrystal compounds each containing an optically active group, and as aresult, the present invention has been reached.

Most of the compounds having the above-mentioned general formula (I) cansingly show a chiral smectic C phase which is important as aferroelectric liquid crystal phase.

Some of the compounds having the general formula (I) show the smectic Aphase and/or chiral nematic (cholesteric) phase only but do not exhibitany chiral smectic C phase, or some of them do not show the liquidcrystal phase singly. Such compounds may be blended with other compoundshaving the general formula (I), other chiral smectic liquid crystalcompounds, or other smectic liquid crystal compounds, so that they canbe used as the liquid crystal compositions showing ferroelectriccharacteristics.

In the general formula (I), the naphthalene ring is substitutied by thegroups A and B preferably at 1- and 4-positions, 1- and 5-positions or2- and 6-positions thereof, more preferably at 2- and 6-positionsthereof.

The group X in the general formula (I) is preferably a hydrogen atom, ahalogen atom, a methyl group or a cyano group.

With regard to the general formula (I), each of Z₁, Z₂, Z₃ and Z₄ in thegroups A and B can be selected from the group consisting of a singlebond, --C(O)--, --O--, --CH₂ --, --CH═N--, --N═CH--, --CH═CH--,--C.tbd.C--, --N═N--and --N(O)═N--. However, taking photochemical orchemical stabilities into consideration, the single bond, --C(O)--,--O--or --CH₂ --is preferable, and it is more preferred that each of the--Z₁ --Z₂ -- and --Z₃ --Z₄ --groups is the single bond, --C(O)--O--,--O--C(O)--, --CH₂ O--or --OCH₂ --.

Each of the C and D rings can be optionally selected from the groupconsisting of 1,4-phenylene, 2,6-naphthylene, pyrimidine-2,5-diyl,trans-1,4-cyclohexylene, trans-1,3-dioxan-2, 5-diyl,trans-1,3-oxathian-2,5-diyl, trans-1,3-dithian-2,5-diyl,1,3,2-dioxaborinane-2,5-diyl and groups in which hydrogen atom in eachof these groups is monosubstituted or multisubstituted by X. However,these groups preferably are 1,4-phenylene, 2,6-naphthylene,pyrimidine-2,5-diyl, trans-1,4-cyclohexylene,1,3,2-dioxaborinane-2,5-diyl and groups in which they are substituted byX, and more preferably they are 1,4-phenylene, 2,6-naphthylene,trans-1,4-cyclohexylene and groups in which they are substituted by X.

Each of m and n in the groups A and B is an integer of 0, 1 or 2, butpreferably they are such balues as to satisfy the relation of m+n≦2.

In the compounds represented by the general formula (I), particularlypreferable ones can be recited in general formulae as follows: ##STR11##

Concrete examples of this type can be enumerated in general formulae asfollows: ##STR12##

Concrete examples of this type can be enumerated in general formula asfollows: ##STR13##

Concrete examples of this type can be enumerated in general formula asfollows: ##STR14##

Concrete examples of this type can be enumerated in general formula asfollows: ##STR15##

Concrete examples of this type can be enumerated in general formula asfollows: ##STR16##

Concrete examples of this type can be enumerated in general formula asfollows: ##STR17##

In the above-mentioned formulae, R₁ and R₂ are independent and arerespectively --R, --OR, --C(O)--OR-- or --O--C(O)--R-- and at least oneof them contains an optically active group, in which groups R is ahydrogen atom, a halogen atom, a cyano group or a straight-chain orbranched alkyl group, an alkoxyalkyl group, a halogenoalkyl group, acyanoalkyl group, an alkenylalkyl group or an alkoxycarbonylalkyl group,latter six groups each having 1 to 20 carbon atoms; each of X₁ to X₆ isa hydrogen atom, a halogen atom, a methyl group or a cyano group; and Zis a single bond, --C(O)--O--, --O--C(O)--, --CH₂ O-- or --OCH₂ --.

In the compound having the general formula (I), there exists at leastone asymmetric carbon atom, but this atom preferably is present in thegroup Y of the group A and/or B. The group Y is a hydrogen atom, ahalogen atom, a cyano group, a straight-chain or branched alkyl group oran alkenylalkyl group, the latter two groups each having 1 to 20 carbonatoms, and one CH₂ group or two unadjacent CH₂ groups in each of thesealkyl groups may be substituted by --O--, --C(O)--, --O--C(O)--or--C(O)--O--, and one hydrogen atom in each of the alkyl groups may besubstituted by a halogen atom, a cyano group or an alkoxyl group.Preferably, the group Y is a hydrogen atom, a halogen atom, a cyanogroup, a straight-chain or branched alkyl group or an alkenylalkylgroup, the latter two groups each having 1 to 20 carbon atoms ( one CH₂group or two unadjacent CH₂ groups in its alkyl portion may besubstituted by --O--or --C(O)--O--, and one hydrogen atom in the alkylportion may be substituted by a halogen atom, a cyano group or analkoxyl group).

As an asymmetric carbon source, all optically active materials areusable, but in particular, optically active alcohols and opticallyactive carboxylic acids are useful as the starting materials.

Examples of the useful optically active alcohols include opticallyactive 2-methylbutanol, optically active 3-methylpentanol, opticallyactive 4-methylhexanol, optically active 5-methylheptanol, opticallyactive 6-methyloctanol, optically active citronellol, optically active3,7-dimethyloctanol, optically active 2-butanol, optically active2-pentanol, optically active 2-hexanol, optically active 2-heptanol,optically active 2-octanol, optically active 2-nonanol, optically active2-decanol, optically active 2-undecanol, optically active 2-dodecanol,optically active 2-methylpentanol, optically active 2-methylhexanol,optically active 2-alkyloxypropanol, optically active 3-alkyloxybutanol,optically active 3-alkyloxypentanol, optically active lactates,optically active 3-hydroxy-2-methylpropanoates, optically active3-hydroxybutanoates, optically active 3-hydroxypentanoates, opticallyactive 2-halogenopropanol, optically active 2-halogenobutanol, opticallyactive 2-halogenopentanol, optically active 2-halogenohexanol, opticallyactive 2-halogenoheptanol, optically active 2-halogenooctanol, opticallyactive 2-halogenononanol, optically active 2-halogenodecanol, opticallyactive 2-halogenoundecanol, optically active 2-halogenododecanol andoptically active cyanoalkylcarbinol.

Examples of the useful optically active carboxylic acids includeoptically active 2-methylbutanoic acid, optically active3-methylpentanoic acid, optically active 4-methylhexanoic acid,optically active 2-methylpentanoic acid, optically active3,7-dimethyloctanoic acid, optically active 3-methyl-2-halogenopentanoicacid, optically active 4-methyl-2-halogenobutanoic acid, opticallyactive 2-alkyloxypropanoic acid, optically active 3-alkyloxybutanoicacid and optically active 3-alkyloxypentanoic acid.

The liquid crystal composition according to the present invention may beconstituted by combining two or more kinds of compounds regarding thepresent invention which are represented by the general formula (I), butit can also be prepared by joining the compound of the present inventionto the following general formula (II).

The compound of the present invention having the general formula (I) andshowing the chiral smectic C phase singly is preferably contained in aproportion of 5 wt % or more as a constitutional component in the liquidcrystal composition. When this compound is present in the amount of 10wt % or more in a known liquid crystal compound, a response speed of theknown compound can be noticeably accelerated. The constitutionalcomponent showing no SC* phase is preferably present therein in aproportion of less than 50 wt %. ##STR18## wherein E and F rings areindependent and are ##STR19## in which G is a hydrogen atom, a halogenatom, a cyano group or a methyl group; each of a and b is an integer of0, 1 or 2; each of X₁, X₂ and X₃ is a single bond, --O--, --C(O)--O--,--O--C(O)--, --CH₂ O--, --OCH₂ -- or --CH₂ CH₂ --; and each of R and R'is a hydrogen atom, a halogen atom, a cyano group, an alkyl group, analkoxyl group, an optically active alkyl group, an optically activealkoxyl group, an optically active alkoxyalkyl group, an opticallyactive alkenylalkyl group or an optically active halogenoalkyl group,the latter seven groups each having 1 to 20 carbon atoms.

The compound of the general formula (I) can be manufactured inaccordance with the combination of known unit operations described in aliterature (e.g. a standard academic literature such as "Methoden derOrganischen Chemie" written by Houben Weil). In addition, knownvariations of the manufacturing methods which are not referred to inthis specification can also be employed.

In the case that --Z₁ --Z₂ -- of A and/or B in the formula (I) is--C(O)--O-- and/or --O--C(O)--, raw materials preferably arecombinations of compounds having formulae (III) and (IV) ##STR20## withcompounds having formulae (V) to (VIII) ##STR21## wherein X, Z₁, Z₂, Z₃,Z₄, rings C and D as well as Y are as defined above.

That is, when a compound of the formula (III) is combined with acompound of the formula (VI or (VIII), or when a compound of the formula(IV) is combined with a compound of the formula (V) or (VII), thecompound of the general formula I) can be prepared in accordance with anesterification process which is usually used. This process comprises,for example, the steps of first changing the carboxylic compound of theformula (IV), (VI or (VIII) into a reactive derivative such as acorresponding carboxylic acid halide (in particular, chloride orbromide) or carboxylic anhydride and afterward allowing the same toreact with the compound of the formula (III), (V) or (VII).

In the case that --Z₁ --Z₂ -- of A and/or B in the formula (I) is --CH₂O-- and/or --O--CH₂ --, raw materials preferably are combinations ofcompounds having formulae (III), (V) and (VII) with compounds having thefollowing formulae (IX), (X) and (XI) ##STR22##

In the present invention, the reaction of a usual etherification can beused, and for example, the compound regarding the present invention canbe prepared by reacting a hydroxyl compound with a reactive alkylderivative such as a halide in the presence of a base (sodium hydroxide,potassium hydroxide, sodium hydride, potassium hydride or

Table 2 sets forth typical examples of the compounds regarding thepresent invention.

As will be definite from examples given hereinafter, the presentinvention intends to provide optically active naphthalene derivativecompounds represented by the general formula (I) and ferroelectricsmectic liquid crystal compositions each containing at least onederivative compound mentioned above, whereby the present invention hasan effect capable of providing rapidly responsive display elementshaving photostability and chemical stability.

                                      TABLE 2                                     __________________________________________________________________________     ##STR23##                                                                    Example                                                                       Compound                                                                      No.   R.sup.1        X.sub.1                                                                           X.sub.2                                                                         X.sub.3                                                                           X.sub.4                                                                            Z       R.sub.2                           __________________________________________________________________________    1     CH.sub.3 O     H   H H   H    COO     COOCH.sub.2 C*H(CH.sub.3)C.sub                                                .2 H.sub.5                        2     C.sub.4 H.sub.9 O                                                                            H   H H   H    "       "                                 3     C.sub.6 H.sub.13 O                                                                           H   H H   H    "       "                                 4     C.sub.7 H.sub.15 O                                                                           H   H H   H    "       "                                 5     C.sub.8 H.sub.17 O                                                                           H   H H   H    "       "                                 6     C.sub.9 H.sub.19 O                                                                           H   H H   H    "       "                                 7     C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 8     C.sub.11 H.sub.23 O                                                                          H   H H   H    "       "                                 9     C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 10    C.sub.13 H.sub.27 O                                                                          H   H H   H    "       "                                 11    C.sub.14 H.sub.29 O                                                                          H   H H   H    "       "                                 12    C.sub.15 H.sub.31 O                                                                          H   H H   H    "       "                                 13    C.sub.16 H.sub.33 O                                                                          H   H H   H    "       "                                 14    C.sub.18 H.sub.37 O                                                                          H   H H   H    "       "                                 15    C.sub.20 H.sub.41 O                                                                          H   H H   H    "       "                                 16    C.sub.4 H.sub.9 O                                                                            F   H H   H    "       "                                 17    C.sub.8 H.sub.17 O                                                                           F   H H   H    "       "                                 18    C.sub.9 H.sub.19 O                                                                           F   H H   H    "       "                                 19    C.sub.10 H.sub.21 O                                                                          F   H H   H    "       "                                 20    C.sub.12 H.sub.25 O                                                                          F   H H   H    "       "                                 21    C.sub.16 H.sub.33 O                                                                          F   H H   H    "       "                                 22    C.sub.8 H.sub.17 O                                                                           Cl  H H   H    "       "                                 23    C.sub.10 H.sub.21 O                                                                          Cl  H H   H    "       "                                 24    C.sub.12 H.sub.25 O                                                                          Cl  H H   H    COO     COOCH.sub.2 C*H(CH.sub.3)C.sub                                                .2 H.sub.5                        25    C.sub.8 H.sub.17 O                                                                           H   H CN  H    "       "                                 26    C.sub.10 H.sub.21 O                                                                          Br  H H   H    "                                                                                      ##STR24##                        27    C.sub.7 H.sub.15                                                                             CN  H H   H    "COOC*H(CH.sub.3)C.sub.6 H.sub.13         28    C.sub.8 H.sub.17 O                                                                           H   F H   H    "       "                                 29    C.sub.10 H.sub.21 O                                                                          F   H H   H    "       "                                 30    C.sub.12 H.sub.25 O                                                                          F   H H   H    "       COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                          31    C.sub.9 H.sub.19 O                                                                           F   H H   H    "       COOC*H(CH.sub.3)C.sub.2                                                       H.sub.5                           32    C.sub.12 H.sub.25 O                                                                          F   H H   H    "       "                                 33    C.sub.9 H.sub.19                                                                             OCH.sub.3                                                                         H H   H    "       "                                 34    C.sub.10 H.sub.21 O                                                                          F   H H   H    "       COOC*H(CH.sub.3)C.sub.3                                                       H.sub.7                           35    C.sub.12 H.sub.25 O                                                                          F   H H   H    "       "                                 36    C.sub.6 H.sub.13 O                                                                           F   H H   H    "       COO(CH.sub.2).sub.2 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                37    C.sub.11 H.sub.23 O                                                                          F   H H   H    "       "                                 38    C.sub.10 H.sub.21 O                                                                          F   H H   H    "       COO(CH.sub.2).sub.3 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                39    C.sub.12 H.sub.25 O                                                                          F   H H   H    "       "                                 40    C.sub.12 H.sub.25 O                                                                          F   H H   H    "       COO(CH.sub.2).sub.4 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                41    C.sub.12 H.sub.25 O                                                                          F   H H   H    "       COO(CH.sub.2).sub.5 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                42    C.sub.14 H.sub.29 O                                                                          F   H H   H    "       COO(CH.sub.                                                                   2).sub.5 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                           43    C.sub.10 H.sub.21 O                                                                          H   H Cl  H    "       COOCH.sub.2 C*H(CH.sub.3)C.sub                                                .2 H.sub.5                        44    C.sub.14 H.sub.29 O                                                                          H   H Cl  H    "       "                                 45    C.sub.16 H.sub.33 O                                                                          H   H Cl  H    "       "                                 46    C.sub.8 H.sub.17 O                                                                           H   H H   H    "       COO(CH.sub.2).sub.2 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                47    C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 48    C.sub.8 H.sub.17 O                                                                           H   H H   H    COO     COO(CH.sub.2).sub.3 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                49    C.sub.9 H.sub.19 O                                                                           H   H H   H    "       "                                 50    C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 51    C.sub.11 H.sub.23 O                                                                          H   H H   H    "       COO(CH.sub.2).sub.3 C*H(CH.sub                                                .3 C.sub.2 H.sub.5                52    C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 53    C.sub.13 H.sub.27 O                                                                          H   H H   H    "       "                                 54    C.sub.14 H.sub.29 O                                                                          H   H H   H    "       "                                 55    C.sub.15 H.sub.31 O                                                                          H   H H   H    "       "                                 56    C.sub.8 H.sub.17 O                                                                           H   H H   H    "       COO(CH.sub.2).sub.4 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                57    C.sub.9 H.sub.19 O                                                                           H   H H   H    "       COO(CH.sub.2).sub.5 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                58    C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 59    C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 60    C.sub.10 H.sub.21 O                                                                          H   H H   H    "       COOCH.sub.2 C*H(CH.sub.3)C.sub                                                .3 H.sub.7                        61    C.sub.12 H.sub.25 O                                                                          H   H H   H    "       COOCH.sub.2 C*H(CH.sub.3)C.sub                                                .4 H.sub.9                        62    C.sub.8 H.sub.17 O                                                                           H   H H   H    "                                                                                      ##STR25##                        63    C.sub.10 H.sub. 21 O                                                                         H   H H   H    "       "                                 64    C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 65    C.sub.4 H.sub.9 O                                                                            H   H H   H    "       COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                          66    C.sub.6 H.sub.13 O                                                                           H   H H   H    "       "                                 67    C.sub.8 H.sub.17 O                                                                           H   H H   H    "       "                                 68    C.sub.9 H.sub.19 O                                                                           H   H H   H    "       "                                 69    C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 70    C.sub.11 H.sub.23 O                                                                          H   H H   H    "       "                                 71    C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 72    C.sub.14 H.sub.29 O                                                                          H   H H   H    COO     COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                          73    C.sub.16 H.sub.33 O                                                                          H   H H   H    "       "                                 74    C.sub.20 H.sub.41 O                                                                          H   H H   H    "       "                                 75    C.sub.13 H.sub.27 O                                                                          H   H H   H    "       "                                 76    C.sub.4 H.sub.9 O                                                                            H   H H   H    "       COOC*H(CH.sub.3)C.sub.2                                                       H.sub.5                           77    C.sub.7 H.sub.15 O                                                                           H   H H   H    "       "                                 78    C.sub.9 H.sub.19 O                                                                           H   H H   H    "       "                                 79    C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 80    C.sub.11 H.sub.23 O                                                                          H   H H   H    "       "                                 81    C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 82    C.sub.14 H.sub.29 O                                                                          H   H H   H    "       "                                 83    C.sub.16 H.sub.33 O                                                                          H   H H   H    "       "                                 84    C.sub.2 H.sub.5 O                                                                            H   H H   H    "       COOC*H(CH.sub.3)C.sub.3                                                       H.sub.7                           85    C.sub.4 H.sub.9 O                                                                            H   H H   H    "       "                                 86    C.sub.8 H.sub.17 O                                                                           H   H H   H    "       "                                 87    C.sub.9 H.sub.19 O                                                                           H   H H   H    "       "                                 88    C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 89    C.sub.11 H.sub.23 O                                                                          H   H H   H    "       "                                 90    C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 91    C.sub.16 H.sub.33 O                                                                          H   H H   H    "       "                                 92    C.sub.10 H.sub.21 O                                                                          H   H H   H    "       COOC*H(CH.sub.3)C.sub.4                                                       H.sub.9                           93    C.sub.12 H.sub.25 O                                                                          H   H H   H    "       COOC*H(CH.sub.3)C.sub.5                                                       H.sub.11                          94    C.sub.10 H.sub.21 O                                                                          H   H H   H    "       COOC*H(CH.sub.3)C.sub.7                                                       H.sub.15                          95    C.sub.8 H.sub.17 O                                                                           H   H H   H    "       COOC*H(CH.sub.3)C.sub.8                                                       H.sub.17                          96    C.sub.9 H.sub.19 O                                                                           H   H H   H    COO     COOC*H(CH.sub.3)C.sub.10                                                      H.sub.21                          97    C.sub.9 H.sub.19 O                                                                           H   H H   H    "       COOCH.sub.2 C*H(F)C.sub.3                                                     H.sub.7                           98    C.sub.11 H.sub.23 O                                                                          H   H H   H    "       COOCH.sub.2 C*H(F)C.sub.5                                                     H.sub.11                          99    C.sub.8 H.sub.17 O                                                                           H   H H   H    "       COOCH.sub.2 C*H(F)C.sub.7                                                     H.sub.15                          100   C.sub.12 H.sub.25 O                                                                          H   H H   H    "       COOCH.sub.2 C*H(F)C.sub.10                                                    H.sub.21                          101   C.sub.7 H.sub.15 O                                                                           H   H H   H    "       COOCH.sub.2 C*H(OCH.sub.3)CH.s                                                ub.3                              102   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       COOCH.sub.2 C*H(OC.sub.3                                                      H.sub.7)CH.sub.3                  103   C.sub.5 H.sub.11                                                                             Br  H H   H    "       COOCH.sub.2 C*H(CH.sub.3)C.sub                                                .2 H.sub.5                        104   C.sub.8 H.sub.17                                                                             H   H H   H    "       COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                          105   C.sub.4 H.sub.9 O(CH.sub.2).sub.4 O                                                          H   H H   H    "       "                                 106   C.sub.6 H.sub.13 C*H(CH.sub.3)O                                                              H   H H   H    "       COOCH.sub.2 C*H(CH.sub.3)C.sub                                                .2 H.sub.5                        107   C.sub.3 H.sub.7 O                                                                            H   H H   H    "       OCH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                          108   C.sub.6 H.sub.13 O                                                                           H   H H   H    "       "                                 109   C.sub.8 H.sub.17 O                                                                           H   H H   H    "       "                                 110   C.sub.9 H.sub.19 O                                                                           H   H H   H    "       "                                 111   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 112   C.sub.11 H.sub.23 O                                                                          H   H H   H    "       "                                 113   C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 114   C.sub.13 H.sub.27 O                                                                          H   H H   H    "       "                                 115   C.sub.14 H.sub.29 O                                                                          H   H H   H    "       "                                 116   C.sub.15 H.sub.31 O                                                                          H   H H   H    "       "                                 117   C.sub.16 H.sub.33 O                                                                          H   H H   H    "       "                                 118   C.sub.8 H.sub.17                                                                             H   H H   H    "       "                                 119   C.sub.8 H.sub.17 O                                                                           CN  H H   H    "       "                                 120   C.sub.10 H.sub.21 O                                                                          H   H C.sub.2 H.sub.5                                                                   H    COO     OCH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                          121   C.sub.12 H.sub.25 O                                                                          H   H OCH.sub.3                                                                         H    "       "                                 122   C.sub.6 H.sub.13 O                                                                           H   H H   H    "       O(CH.sub.2).sub.3 C*H(CH.sub.3                                                )C.sub.2 H.sub.5                  123   C.sub.8 H.sub.17 O                                                                           H   H H   H    "       O(CH.sub.2).sub.3 C*H(CH.sub.3                                                )C.sub.2 H.sub.5                  124   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 125   C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 126   C.sub.14 H.sub.29 O                                                                          H   H H   H    "       "                                 127   C.sub.16 H.sub.33 O                                                                          H   H H   H    "       "                                 128   C.sub.8 H.sub.17                                                                             H   H H   H    "       "                                 129   C.sub.10 H.sub.21 O                                                                          H   H H   Cl   "       O(CH.sub.2).sub.2 C*H(CH.sub.3                                                )C.sub.2 H.sub.5                  130   C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 131   C.sub.3 H.sub.7 O                                                                            H   H H   H    "       OC*H(CH.sub.3)C.sub.6                                                         H.sub.13                          132   C.sub.7 H.sub.15 O                                                                           H   H H   H    "       "                                 133   C.sub.8 H.sub.17 O                                                                           H   H H   H    "       "                                 134   C.sub.9 H.sub.19 O                                                                           H   H H   H    "       "                                 135   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 136   C.sub.11 H.sub.23 O                                                                          H   H H   H    "       "                                 137   C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 138   C.sub.13 H.sub.27 O                                                                          H   H H   H    "       "                                 139   C.sub.14 H.sub.29 O                                                                          H   H H   H    "       "                                 140   C.sub.9 H.sub.19 O                                                                           H   H H   H    "       OC*H(CH.sub.3)C.sub.2                                                         H.sub.5                           141   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 142   C.sub.12 H.sub.25 O                                                                          H   H H   H    "       OC*H(CH.sub.3)C.sub.3                                                         H.sub.7                           143   C.sub.8 H.sub.17 O                                                                           H   H H   H    "       OCH.sub.2 C*H(OCH.sub.3)CH.sub                                                .3                                144   C.sub.8 H.sub.17 O                                                                           H   H H   H    COO     OCH.sub.2 C*H(OC.sub.2                                                        H.sub.5)CH.sub.3                  145   C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 146   C.sub.9 H.sub.19 O                                                                           H   H H   H    "       OCH.sub.2 C*H(OC.sub.3                                                        H.sub.7)CH.sub.3                  147   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 148   C.sub.12 H.sub.25 O                                                                          H   H H   H    "       O(CH.sub.2).sub.2 C*H(OC.sub.5                                                 H.sub.11)CH.sub.3                149   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       O(CH.sub.2).sub.2 C*H(OC.sub.2                                                 H.sub.5)C.sub.2 H.sub.5          150   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       OCH.sub.2 C*H(F)C.sub.5                                                       H.sub.11                          151   C.sub.2 H.sub.5 C*H(CH.sub.3)CH.sub.2 O                                                      H   H H   H    "       OC.sub.10 H.sub.21                152   C.sub.6 H.sub.13 C*H(CH.sub.3)O                                                              H   H H   H    "       OC.sub.10 H.sub.21                153   C.sub.2 H.sub.5 C*H(CH.sub.3)(CH.sub.2).sub.3 O                                              H   H H   H    "       OC.sub.10 H.sub.21                154   C.sub.8 H.sub.17 O                                                                           H   H H   H    "       OCOC*H(CH.sub.3)C.sub.2                                                       H.sub.5                           155   C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 156   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       OCOC*H(OCH.sub.3)CH.sub.3         157   C.sub.8 H.sub.17 O                                                                           H   H H   H    "       COCH.sub.2 CH.sub.2 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                158   H              H   H H   H    CH.sub.2 O                                                                            COOCH.sub.2 C*H(CH.sub.3)C.sub                                                .2 H.sub.5                        159   H              H   H H   H    "                                                                                      ##STR26##                        160   C.sub.8 H.sub.17 O                                                                           H   H H   H    "                                                                                      ##STR27##                        161   H              H   H H   H    "       COO(CH.sub.2).sub.2 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                162   H              H   H H   H    "       COO(CH.sub.2).sub.3 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                163   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 164   H              H   H H   H    "       COO(CH.sub.2).sub.5 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                165   H              H   H H   H    "       COOC*H(CH.sub.3)C.sub.2                                                       H.sub.5                           166   C.sub.4 H.sub.9 O                                                                            H   H H   H    "       "                                 167   C.sub.8 H.sub.17 O                                                                           H   H H   H    "       "                                 168   H              H   H H   H    CH.sub.2 O                                                                            COOC*H(CH.sub.3)C.sub.3                                                       H.sub.7                           169   C.sub.6 H.sub.13 O                                                                           H   H H   H    "       "                                 170   H              H   H H   H    "       COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                          171   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 172   C.sub.8 H.sub.17 O                                                                           H   H H   H    "       COOCH.sub.2 C*H(F)C.sub.4                                                     H.sub.9                           173   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       COOCH.sub.2 C*H(F)C.sub.6                                                     H.sub.13                          174   C.sub.9 H.sub.19 O                                                                           H   H H   H    OCH.sub.2                                                                             COOCH.sub.2 C*H(CH.sub.3)C.sub                                                .2 H.sub.5                        175   C.sub.10 H.sub. 21 O                                                                         H   H H   H    "       COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                          176   C.sub.2 H.sub.5 C*H(CH.sub.3)CH.sub.2 O                                                      H   H H   H    OCO     OC.sub.6 H.sub.13                 177   "              H   H H   H    "       OC.sub.8 H.sub.17                 178   "              H   H H   H    "       OC.sub.10 H.sub.21                179   "              H   H H   H    "       OC.sub.13 H.sub.27                180   C.sub.2 H.sub.5 C*H(CH.sub.3)(CH.sub.2).sub.3 O                                              H   H H   H    "       OC.sub.6 H.sub.13                 181   "              H   H H   H    "       OC.sub.8 H.sub.17                 182   "              H   H H   H    "       OC.sub.10 H.sub.21                183   "              H   H H   H    "       OC.sub.12 H.sub.25                184   "              H   H H   H    "       OC.sub.14 H.sub.29                185   C.sub.6 H.sub.13 C*H(CH.sub.3)O                                                              H   H H   H    "       OC.sub.8 H.sub.17                 186   C.sub.2 H.sub.5 C*H(CH.sub.3)O                                                               H   H H   H    "       OC.sub.10 H.sub. 21               187   C.sub.2 H.sub.5 C*H(CH.sub.3)CH.sub.2                                                        H   H H   H    "       C.sub.4 H.sub.9                   188   "              H   H H   H    "       C.sub.7 H.sub.15                  189   C.sub.6 H.sub.13 O                                                                           H   H H   H    "       OCH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                          190   C.sub.8 H.sub.17 O                                                                           H   H H   H    "       "                                 191   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 192   C.sub.12 H.sub.25 O                                                                          H   H H   H    "       OCH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                          193   C.sub.6 H.sub.13 O                                                                           H   H H   H    OCO     O(CH.sub.2).sub.3 C*H(CH.sub.3                                                )C.sub.2 H.sub.5                  194   C.sub.8 H.sub.17 O                                                                           H   H H   H    "       "                                 195   C.sub.10 H.sub.21 O                                                                          H   H H   H    "       "                                 196   C.sub.12 H.sub.25 O                                                                          H   H H   H    "       "                                 197   C.sub.8 H.sub.17 O                                                                           H   H H   H    "       OC*H(CH.sub.3)C.sub.6                                                         H.sub.13                          198   F              H   H H   H    "       "                                 199   CN             H   H H   H    "       "                                 200   Cl             H   H H   H    "       "                                 201   CN             F   H H   H    "       "                                 202   C.sub.2 H.sub.5 C*H(CH.sub.3)CH.sub.2 OCO                                                    H   H H   H    "       OC.sub.8 H.sub.17                 203   "              H   H H   H    "       OC.sub.10 H.sub.21                204   "              H   H H   H    "       OC.sub.12 H.sub.25                205   "              H   H H   H    "       OC.sub.14 H.sub.29                206   C.sub.3 H.sub.7 C*H(CH.sub.3)OCO                                                             H   H H   H    "       OC.sub.10 H.sub.21                207   "              H   H H   H    "       OC.sub.12 H.sub.25                208   C.sub.2 H.sub.5 C*H(CH.sub.3)(CH.sub.2).sub.3 OCO                                            H   H H   H    "       OC.sub.4 H.sub.9                  209   "              H   H H   H    "       OC.sub.6 H.sub.13                 210   "              H   H H   H    "       OC.sub.8 H.sub.17                 211   "              H   H H   H    "       OC.sub.10 H.sub.21                212   "              H   H H   H    "       OC.sub.12 H.sub.25                213   "              H   H H   H    "       OC.sub.14 H.sub.29                214   "              H   H H   H    "       OC.sub.16 H.sub.33                215   C.sub.2 H.sub.5 C*H(CH.sub.3)OCO                                                             H   H H   H    "       OC.sub.12 H.sub.25                216   "              H   H H   H    "       O(CH.sub.2).sub.2 OC.sub.4                                                    H.sub.9                           217   C.sub.4 H.sub.9 C*H(CH.sub.3)OCO                                                             H   H H   H    "       OC.sub.8 H.sub.17                 218   C.sub.4 H.sub.9 C*H(CH.sub.3)OCO                                                             H   H H   H    OCO     OC.sub.9 H.sub.19                 219   "              H   H H   H    "       OC.sub.10 H.sub.21                220   C.sub.5 H.sub.11 C*H(CH.sub.3)OCO                                                            H   H H   H    "       OC.sub.7 H.sub.15                 221   "              H   H H   H    "       OC.sub.9 H.sub.19                 222   "              H   H H   H    "       OC.sub.11 H.sub.23                223   CH.sub.3 C*H(OC.sub.2 H.sub.5)CH.sub.2 O                                                     H   H H   H    "       OC.sub.8 H.sub.17                 224   CH.sub.3 C*H(OC.sub.4 H.sub.9)CH.sub.2 O                                                     H   H H   H    "       OC.sub.10 H.sub.21                225   C.sub.2 H.sub.5 C*H(F)CH.sub.2 OCO                                                           H   H H   H    "       OC.sub.7 H.sub.15                 226   C.sub.4 H.sub.9 C*H(F)CH.sub.2 OCO                                                           H   H H   H    "       OC.sub.10 H.sub.21                227   C.sub.10 H.sub.21 O                                                                          H   H H   H    CH.sub.2 CH.sub.2                                                                     OCH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                          228   C.sub.9 H.sub.19 O                                                                           H   H H   H    CHN     (CH.sub.2).sub.3 C*H(CH.sub.3)                                                C.sub.2 H.sub.5                   229   C.sub.7 H.sub.15 O                                                                           F   H H   H    CHCH    OC*H(CH.sub.3)C.sub.6                                                         H.sub.13                          230   C.sub.11 H.sub.23 O                                                                          H   H H   H    CC      CH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                           __________________________________________________________________________     ##STR28##                                                                    Example                                                                       Compound                                                                      No.   R.sub.1          X.sub.1                                                                         X.sub.2                                                                           X.sub.3                                                                         X.sub.4                                                                           X.sub.5                                                                         X.sub.6                                                                           Z     R.sub.2                        __________________________________________________________________________    231   CH.sub.3 O       H H   H H   H H   COO   COOCH.sub.2 C*H(CH.sub.3)C.                                                   sub.2 H.sub.5                  232   C.sub.8 H.sub.17 O                                                                             H H   H H   H H   "     "                              233   C.sub.8 H.sub.17 O                                                                             H H   H H   Cl                                                                              H   "     "                              234   C.sub.12 H.sub.25 O                                                                            H F   H H   H H   "     "                              235   C.sub.7 H.sub.15 O                                                                             H H   H H   H H   "     COOC*H(CH.sub.3)C.sub.2                                                       H.sub.5                        236   C.sub.8 H.sub.17 O                                                                             H H   H H   H H   "     "                              237   C.sub.13 H.sub.27 O                                                                            Cl                                                                              H   H H   H H   "     "                              238   C.sub.7 H.sub.15 H H   H H   H H   "     "                              239   C.sub.8 H.sub.17 H H   H H   H H   "     "                              240   C.sub.12 H.sub.25                                                                              H H   H H   H H   "     "                              241   C.sub.7 H.sub.15 O                                                                             H H   H H   H H   "     COOC*H(CH.sub.3)C.sub.3                                                       H.sub.7                        242   C.sub.10 H.sub.21 O                                                                            H H   H H   H H   "     COOC*H(CH.sub.3)C.sub.4                                                       H.sub.9                        243   C.sub.4 H.sub.9 O                                                                              H H   H H   H H   "     COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                       244   C.sub.7 H.sub.15 O                                                                             H H   H H   H H   "     "                              245   C.sub.8 H.sub.17 O                                                                             H H   H H   H H   "     "                              246   C.sub.10 H.sub.21 O                                                                            H H   H H   H H   "     "                              247   C.sub.12 H.sub.25 O                                                                            H H   H H   H H   "     "                              248   C.sub.7 H.sub.15 H H   H H   H H   "     "                              249   C.sub.8 H.sub.17 H H   H H   H H   "     "                              250   C.sub.10 H.sub.21                                                                              H H   H H   H H   "     "                              251   C.sub.7 H.sub.15 O                                                                             Cl                                                                              H   H H   H H   "     "                              252   C.sub.9 H.sub.19 O                                                                             Cl                                                                              H   H H   H H   "     "                              253   C.sub.10 H.sub.21 O                                                                            F H   H H   H H   "     "                              254   C.sub.12 H.sub.25 O                                                                            F H   H H   H H   COO   COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                       255   C.sub.12 H.sub.25 O                                                                            H H   H F   H H   "     "                              256   C.sub.8 H.sub.17 O                                                                             H H   H H   H H   "     COOC*H(CH.sub.3)C.sub.8                                                       H.sub.17                       257   C.sub.7 H.sub.15 H H   H H   H H   "     "                              258   C.sub.12 H.sub.25 O                                                                            H H   H H   H H   "     COOC*H(CH.sub.3)C.sub.10                                                      H.sub.21                       259   C.sub.10 H.sub.21 O                                                                            H H   H H   H H   "     COO(CH.sub.2).sub.3                                                           C*H(CH.sub.3)C.sub.2                                                          H.sub.5                        260   C.sub.7 H.sub.15 O                                                                             H H   H H   H H   "     COOCH.sub.2 C*H(OCH.sub.3)C                                                   H.sub.3                        261   C.sub.9 H.sub.19 O                                                                             H H   H H   H H   "     COOCH.sub.2 C*H(OC.sub.3                                                      H.sub.7)CH.sub.3               262   C.sub.9 H.sub.19 O                                                                             H H   H H   H H   "     COO(CH.sub.2).sub.2                                                           C*H(OC.sub.4 H.sub.9)C.sub.                                                   2 H.sub.5                      263   C.sub.8 H.sub.17 O                                                                             H H   H H   H H   "     COOCH.sub.2 C*H(F)CH.sub.3     264   C.sub.10 H.sub.21 O                                                                            H H   H H   H H   "     COOCH.sub.2 C*H(F)C.sub.6                                                     H.sub.13                       265   C.sub.12 H.sub.25 O                                                                            H H   H H   H H   "     COOCH.sub.2 C*H(F)C.sub.9                                                     H.sub.19                       266   C.sub.4 H.sub.9 O                                                                              H H   H H   H H   "     OCH.sub.2 C*H(CH.sub.3)C.su                                                   b.2 H.sub.5                    267   C.sub.8 H.sub.17 O                                                                             H H   H H   H H   "     "                              268   C.sub.12 H.sub.25 O                                                                            H H   H H   H H   "     "                              269   C.sub.2 H.sub.5 C*H(CH.sub.3)CH.sub.2 O                                                        H H   H H   H H   "     OC.sub.10 H.sub.21             270   C.sub.10 H.sub.21 O                                                                            H H   H H   H H   "     OC*H(CH.sub.3)C.sub.2                                                         H.sub.5                        271   C.sub.5 H.sub.11 O                                                                             H H   H H   H H   "     OC*H(CH.sub.3)C.sub.6                                                         H.sub.13                       272   C.sub.7 H.sub.15 O                                                                             H H   H H   H H   "     "                              273   C.sub.8 H.sub.17 O                                                                             H H   H H   H H   "     "                              274   C.sub.12 H.sub.25 O                                                                            H H   H H   H H   "     "                              275   C.sub.9 H.sub.19 O                                                                             H H   H H   H H   "     OC*H(CH.sub.3)C.sub.3                                                         H.sub.7                        276   C.sub.6 H.sub.13 O                                                                             H H   H H   H H   "                                                                                    ##STR29##                     277   C.sub.10 H.sub.21 O                                                                            H H   H H   H H   "     "                              278   C.sub.8 H.sub.17 O                                                                             H H   H H   H H   COO   O(CH.sub.2).sub.5 C*H(CH.su                                                   b.3)C.sub.2 H.sub.5            279   C.sub.12 H.sub.25 O                                                                            H H   H H   H H   "     OCH.sub.2 C*H(CH.sub.3)C.su                                                   b.4 H.sub.9                    280   C.sub.7 H.sub.15 O                                                                             H H   H H   H H   "     OCH.sub.2 C*H(OC.sub.2                                                        H.sub.5)CH.sub.3               281   C.sub.10 H.sub.21 O                                                                            H H   H H   H H   "     O(CH.sub.2).sub.2 C*H(OC.su                                                   b.3 H.sub.7)C.sub.2                                                           H.sub.5                        282   C.sub.12 H.sub.25 O                                                                            H H   H H   H H   "     OCH.sub.2 C*H(F)C.sub.6                                                       H.sub.13                       283   C.sub.6 H.sub.13 C*H(CH.sub.3)O                                                                H H   H H   H H   "     C.sub.4 H.sub.9                284   "                H H   H H   H H   "     C.sub.6 H.sub.13               285   "                H H   H H   H H   "     C.sub.7 H.sub.15               286   "                H H   H H   H H   "     OC.sub.6 H.sub.13              287   C.sub.18 H.sub.17 O                                                                            H H   H H   H H   "     OCOC*H(CH.sub.3)C.sub.3                                                       H.sub.7                        288   C.sub.8 H.sub.17 H H   H H   H H   "     "                              289   C.sub.10 H.sub.21 O                                                                            H H   H H   H H   "     OCOCH.sub.2 C*H(CH.sub.3)C.                                                   sub.2 H.sub.5                  290   C.sub.2 H.sub.5 C*H(CH.sub.3)CH.sub.2 OCO                                                      H H   H H   H H   OCO   OC.sub.6 H.sub.13              291   C.sub.2 H.sub.5 C*H(CH.sub.3)CH.sub.2 OCO                                                      H H   H H   H H   "     OC.sub.8 H.sub.17              292   C.sub.6 H.sub.13 C*H(CH.sub.3)OCO                                                              H H   H H   H Cl  "     OC.sub.10 H.sub.21             293   C.sub.6 H.sub.13 C*H(CH.sub.3)OCO                                                              H H   H H   H H   "     C.sub.8 H.sub.17               294   C.sub.2 H.sub.5 C*H(CH.sub.3)OCO                                                               H H   F H   H H   "     OC.sub.8 H.sub.17              295   "                H H   H F   H H   "     OC.sub.10 H.sub.21             296   C.sub. 7 H.sub.15 O                                                                            H H   H H   H H   CH.sub.2 O                                                                          COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                       297   C.sub.8 H.sub.17 O                                                                             H H   H H   H H   OCH.sub.2                                                                           "                              298   C.sub.8 H.sub.17 O                                                                             H H   H H   H H   CH.sub.2 O                                                                          COOC*H(CH.sub.3)C.sub.2                                                       H.sub.5                        299   C.sub.10 H.sub.21 O                                                                            H H   H H   H H   OCH.sub.2                                                                           "                              300   C.sub.8 H.sub.17 H H   H H   H H   CH.sub.2 O                                                                          COOCH.sub.2 C*H(CH.sub.3)C.                                                   sub.2 H.sub.5                  301   C.sub.10 H.sub.21                                                                              H H   H H   H H   OCH.sub.2                                                                           "                              __________________________________________________________________________     ##STR30##                                                                    Example                                                                       Compound                                                                      No.     R.sub.1       X.sub.1                                                                         X.sub. 2                                                                            X.sub.3                                                                         X.sub.4                                                                             Z     R.sub.2                           __________________________________________________________________________    302     C.sub.3 H.sub.7 O                                                                           H H     H H     COO   COOCH.sub.2 C*H(CH.sub.3)C.sub                                                .2 H.sub.5                        303     C.sub.6 H.sub.13 O                                                                          H H     H H     "     "                                 304     C.sub.8 H.sub.17 O                                                                          H H     H H     "     "                                 305     C.sub.10 H.sub.21 O                                                                         H H     H H     "     "                                 306     C.sub.12 H.sub.25 O                                                                         H H     H H     "     "                                 307     C.sub.14 H.sub.29 O                                                                         H H     H H     "     "                                 308     C.sub.16 H.sub.33 O                                                                         H H     H H     "     "                                 309     C.sub.9 H.sub.19 O                                                                          H H     H H     "     COOC*H(CH.sub.3)C.sub.2                                                       H.sub.5                           310     C.sub.11 H.sub.23 O                                                                         H H     H H     "     COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                          311     C.sub.10 H.sub.21 O                                                                         Cl                                                                              H     H H     "     COOC*H(CH.sub.3)C.sub.3                                                       H.sub.7                           312     C.sub.8 H.sub.17                                                                            H H     H Cl    "     "                                 313     C.sub.9 H.sub.19                                                                            H H     H H     "     COOCH.sub.2 C*H(OC.sub.3                                                      H.sub.7)CH.sub.3                  314     C.sub.11 H.sub.23 O                                                                         H H     H H     "     COOCH.sub.2 C*H(F)C.sub.6                                                     H.sub.13                          315     C.sub.8 H.sub.17 O                                                                          H H     H H     "     OCH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                          316     C.sub.10 H.sub.21 O                                                                         H H     H H     "     OC*H(CH.sub.3)C.sub.2                                                         H.sub.5                           317     C.sub.10 H.sub.21                                                                           H H     H H     "     OC*H(CH.sub.3)C.sub.6                                                         H.sub.13                          318     C.sub.2 H.sub.5 C*H(CH.sub.3)CH.sub.2 O                                                     H H     H H     "     OC.sub.10 H.sub.21                319     C.sub.2 H.sub.5 C*H(CH.sub.3)(CH.sub.2).sub.3 O                                             H H     H H     "     "                                 320     C.sub.8 H.sub.17 O                                                                          H H     H H     "     OCH.sub.2 C*H(OC.sub.2                                                        H.sub.5)CH.sub.3                  321     C.sub.10 H.sub.21 O                                                                         H H     H H     "     OCH.sub.2 C*H(OC.sub.5                                                        H.sub.11)CH.sub.3                 322     C.sub.7 H.sub.15 O                                                                          H H     H H     "      OCH.sub.2 C*H(F)C.sub.5                                                      H.sub.11                          323     C.sub.9 H.sub.19 O                                                                          H H     H H     "     OCH.sub.2 C*H(F)C.sub.7                                                       H.sub.15                          324     C.sub.6 H.sub.13 O                                                                          H H     H H     "     CH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                           325     C.sub.8 H.sub.17                                                                            H H     H H     COO   CH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                           326     C.sub.6 H.sub.13 C*H(CH.sub.3)O                                                             H H     H H     "     C.sub.6 H.sub.13                  327     "             H H     H H     "     C.sub.8 H.sub.17                  328     "             H H     H H     "     CH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                           329     C.sub.6 H.sub.13 O                                                                          H H     H H     "     OCOC*H(CH.sub.3)C.sub.2                                                       H.sub.5                           330     C.sub.7 H.sub.15                                                                            H H     H H     "     "                                 331     C.sub.10 H.sub.21 O                                                                         H H     H H     "     OCO(CH.sub.2).sub.2 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                332     C.sub.8 H.sub.17                                                                            H H     H H     CH.sub.2 O                                                                          COOCH.sub.2 C*H(CH.sub.3                                                      )C.sub.2 H.sub.5                  333     C.sub.10 H.sub.21 O                                                                         H H     H H     "     "                                 334     C.sub.12 H.sub.25 O                                                                         H H     H H     "     COOC*H(CH.sub.3)C.sub.2                                                       H.sub.5                           335     C.sub.10 H.sub.21 O                                                                         H H     H H     "     COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                          336     C.sub.6 H.sub.13 C*H(CH.sub.3)O                                                             H H     H H     "     COOCH.sub.2 C*H(CH.sub.3)C.sub                                                .2 H.sub.5                        __________________________________________________________________________     ##STR31##                                                                    Example                                                                       Compound                                                                      No.     R.sub.1          X.sub.1                                                                         X.sub.2                                                                              Z     R.sub.2                               __________________________________________________________________________    337     CH.sub.3         H H      COO   COOCH.sub.2 C*H(CH.sub.3)C.sub.2                                              H.sub.5                               338     C.sub.5 H.sub.11 H H      "     "                                     339     C.sub.10 H.sub.21                                                                              H H      "     "                                     340     C.sub.4 H.sub.9  H H      "     COOC*H(CH.sub. 3)C.sub.6 H.sub.13     341     C.sub.9 H.sub.19 H H      "     "                                     342     C.sub.7 H.sub.15 H H      "     COO(CH.sub.2).sub.3 C*H(CH.sub.3)C                                            .sub.2 H.sub.5                        343     C.sub.8 H.sub.17 H H      "     "                                     344     C.sub.5 H.sub.11 H H      "                                                                                    ##STR32##                            345     C.sub.5 H.sub.11 H H      "     COOC*H(CH.sub.3)C.sub.3 H.sub.7       346     C.sub.5 H.sub.11 Cl                                                                              H      "     COOC*H(CH.sub.3)C.sub.2 H.sub.5       347     C.sub.5 H.sub.11 H H      "     COOCH.sub.2 C*H(F)C.sub.6                                                     H.sub.13                              348     C.sub.5 H.sub.11 H H      "     COOCH.sub.2 C*H(OC.sub.2 H.sub.5)C                                            H.sub.3                               349     C.sub.5 H.sub.11 H H      "     OCH.sub.2 C*H(CH.sub.3)C.sub.2                                                H.sub.5                               350     C.sub.7 H.sub.15 H Cl     "     "                                     351     C.sub.3 H.sub.7  H H      "     OC*H(CH.sub.3)C.sub.6 H.sub. 13       352     C.sub.9 H.sub.19 H H      "     "                                     353     C.sub.5 H.sub.11 H H      "     OC*H(CH.sub.3)C.sub.2 H.sub.5         354     C.sub.10 H.sub.21                                                                              H H      "     OC*H(CH.sub.3)C.sub.4 H.sub.9         355     C.sub.5 H.sub.11 H H      "     COOCH.sub.2 C*H(OCH.sub.3)CH.sub.3    356     C.sub.8 H.sub.17 H H      "     COOCH.sub.2 C*H(OC.sub.4 H.sub.9)C                                            H.sub.3                               357     C.sub.4 H.sub.9  H H      "     COOCH.sub.2 C*H(F)C.sub.4                                                     H.sub.9                               358     C.sub.9 H.sub.19 H H      "     COOCH.sub.2 C*H(F)C.sub.8                                                     H.sub.17                              359     C.sub.5 H.sub.11 H H      "     OCOC*H(CH.sub.3)C.sub.2 H.sub.5       360     C.sub.2 H.sub.5 C*H(CH.sub.3)CH.sub.2                                                          H H      COO   C.sub.6 H.sub.13                      361     "                H H      "     OC.sub.5 H.sub.11                     362     "                H H      "     OC*H(CH.sub.3)C.sub.6 H.sub.13        363     C.sub.5 H.sub.11 H H      single bond                                                                         CH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                               364     C.sub.8 H.sub.17 H H      "     OC*H(CH.sub.3)C.sub.6 H.sub.13        365     CH.sub.3         H H      OCO   CH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                               366     C.sub.7 H.sub.15 H H      "     OCH.sub.2 C*H(CH.sub.3)C.sub.2                                                H.sub.5                               367     C.sub.8 H.sub.17 H H      OCO   OC*H(CH.sub.3)C.sub.6 H.sub.13        368     C.sub.5 H.sub.11 H H      "     COOCH.sub.2 C*H(CH.sub.3)C.sub.2                                              H.sub.5                               369     C.sub.7 H.sub.15 H H      "     COOC*H(CH.sub.3)C.sub.6 H.sub.13      370     C.sub.5 H.sub.7  H H      CH.sub.2 O                                                                          "                                     371     C.sub.7 H.sub.15 H H      "     COOC*H(CH.sub.3)C.sub.2 H.sub.5       372     C.sub.8 H.sub.17 H H      "     OCH.sub.2 C*H(CH.sub.3)C.sub.2                                                H.sub.5                               373     C.sub.10 H.sub.21                                                                              H H      "     CH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                               374     C.sub.2 H.sub.5 C*H(CH.sub.3)CH.sub.2                                                          H H      "     C.sub.6 H.sub.13                      375     "                H H      "     OC.sub.8 H.sub.17                     376     C.sub.4 H.sub.9  H H      OCH.sub.2                                                                           OC*H(CH.sub.3)C.sub.2 H.sub.5         377     C.sub.8 H.sub.17 H H      "     OC*H(CH.sub.3)C.sub.6 H.sub.13        __________________________________________________________________________     ##STR33##                                                                    Example                                                                       Compound                                                                      No.   R.sub.1         X.sub.1                                                                         X.sub.2                                                                           X.sub.3                                                                         X.sub.4                                                                           X.sub.5                                                                         X.sub.6                                                                           Z     R.sub.2                         __________________________________________________________________________    378   C.sub.4 H.sub.9 O                                                                             H H   Cl                                                                              H   H H   COO   OCH.sub.2 C*H(CH.sub.3)C.sub                                                  .2 H.sub.5                      379   C.sub.8 H.sub.17 O                                                                            H H   Cl                                                                              H   H H   "     "                               380   C.sub.10 H.sub.21 O                                                                           H H   Cl                                                                              H   H H   "     "                               381   C.sub.12 H.sub.25 O                                                                           H H   Cl                                                                              H   H H   "     "                               382   C.sub.13 H.sub.27 O                                                                           H H   H H   H H   "     "                               383   C.sub.7 H.sub.15 O                                                                            H H   F H   H H   "     "                               384   C.sub.9 H.sub.19 O                                                                            H H   H H   H Cl  "     "                               385   C.sub.10 H.sub.21 O                                                                           H H   H H   F H   "     "                               386   C.sub.8 H.sub.17 O                                                                            Cl                                                                              H   H H   H H   "     "                               387   C.sub.14 H.sub.29 O                                                                           H H   Cl                                                                              H   H H   "     "                               388   C.sub.16 H.sub.33 O                                                                           H H   Cl                                                                              H   H H   "     "                               389   C.sub.8 H.sub.17 O                                                                            H H   H H   H H   "     COOCH.sub.2 C*H(CH.sub.3)C.s                                                  ub.2 H.sub.5                    390   C.sub.8 H.sub.17                                                                              H H   H H   H H   "     "                               391   C.sub.10 H.sub.21 O                                                                           H H   H H   H Cl  "     "                               392   C.sub.10 H.sub.21 O                                                                           H H   H H   H F   "     "                               393   C.sub.12 H.sub.25 O                                                                           H H   H F   H H   "     "                               394   C.sub.10 H.sub.21 O                                                                           H H   H H   H H   "     COOC*H(CH.sub.3)C.sub.2                                                       H.sub.5                         395   C.sub.13 H.sub.27 O                                                                           H H   H H   H H   "     COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                        396   C.sub.10 H.sub.21                                                                             H H   Cl                                                                              H   H H   "     CH.sub.2 C*H(CH.sub.3)C.sub.                                                  2 H.sub.5                       397   C.sub.2 H.sub.5 C*H(CH.sub.3)CH.sub.2 OCO                                                     H H   Cl                                                                              H   H H   OCO   OC.sub.8 H.sub.17               398   "               H H   H F   H H   "     C.sub.10 H.sub.21               399   C.sub.6 H.sub.13 C*H(CH.sub.3)OCO                                                             H Cl  H H   H H   "     OC.sub.10 H.sub.21              400   C.sub.6 H.sub.13 O                                                                            H H   H H   H H   "     OC*H(CH.sub.3)C.sub.6                                                         H.sub.13                        401   C.sub.10 H.sub.21 O                                                                           H H   H H   H H   "     "                               __________________________________________________________________________     ##STR34##                                                                    Example                                                                       Compound                                                                      No.          R.sub.1       X.sub.1 X.sub.2                                                                         R.sub.2                                  __________________________________________________________________________    402          C.sub.3 H.sub.7 O                                                                           H       H COOCH.sub.2 C*H(CH.sub.3)C.sub.2                                              H.sub.5                                  403          C.sub.6 H.sub.13 O                                                                          H       H "                                        404          C.sub.8 H.sub.17 O                                                                          H       H "                                        405          C.sub.9 H.sub.19 O                                                                          H       H "                                        406          C.sub.10 H.sub.21 O                                                                         H       H "                                        407          C.sub.11 H.sub.23 O                                                                         H       H "                                        408          C.sub.12 H.sub.25 O                                                                         H       H "                                        409          C.sub.14 H.sub.29 O                                                                         H       H "                                        410          C.sub.16 H.sub.33 O                                                                         H       H "                                        411          C.sub.18 H.sub.37 O                                                                         H       H "                                        412          C.sub.8 H.sub.17                                                                            H       H "                                        413          C.sub.6 H.sub.13 O                                                                          H       H COOC*H(CH.sub.3)C.sub.2 H.sub.5          414          C.sub.8 H.sub. 17 O                                                                         H       H "                                        415          C.sub.9 H.sub.19 O                                                                          Cl      H "                                        416          C.sub.10 H.sub.21 O                                                                         H       H "                                        417          C.sub.11 H.sub.23 O                                                                         H       H "                                        418          C.sub.12 H.sub.25 O                                                                         H       H "                                        419          C.sub.14 H.sub.29 O                                                                         H       H "                                        420          C.sub.16 H.sub.33 O                                                                         H       H "                                        421          C.sub.18 H.sub.37 O                                                                         H       H "                                        422          C.sub.6 H.sub.13                                                                            H       H "                                        423          C.sub.8 H.sub.17                                                                            H       H "                                        424          C.sub.6 H.sub.13 O                                                                          H       H COOC*H(CH.sub.3)C.sub.3 H.sub.7          425          C.sub.8 H.sub.17 O                                                                          H       H "                                        426          C.sub.10 H.sub.21 O                                                                         H       H "                                        427          C.sub.14 H.sub.29 O                                                                         H       H "                                        428          C.sub.16 H.sub.33 O                                                                         H       H "                                        429          C.sub.18 H.sub.37 O                                                                         H       H "                                        430          C.sub.8 H.sub.17                                                                            H       H "                                        431          C.sub.10 H.sub.21                                                                           H       H "                                        432          C.sub.6 H.sub.13 O                                                                          H       H COOC*H(CH.sub.3)C.sub.4 H.sub.9          433          C.sub.8 H.sub.17 O                                                                          H       H "                                        434          C.sub.10 H.sub.21 O                                                                         H       H "                                        435          C.sub.12 H.sub.25 O                                                                         H       H "                                        436          C.sub.16 H.sub.33 O                                                                         H       H "                                        437          C.sub.8 H.sub.17                                                                            H       H "                                        438          C.sub.10 H.sub.21                                                                           H       H "                                        439          C.sub.8 H.sub.17 O                                                                          H       H COOC*H(CH.sub.3)C.sub.6 H.sub.13         440          C.sub.7 H.sub.15 O                                                                          H       H COO(CH.sub.2).sub.2 C*H(CH.sub.3)C.su                                         b.2 H.sub.5                              441          C.sub.10 H.sub.21 O                                                                         H       H                                                                                ##STR35##                               442          C.sub.10 H.sub.21 O                                                                         H       H COOC*H(CH.sub.3)C.sub.9 H.sub.19         443          C.sub.6 H.sub.13 O                                                                          H       H COOCH.sub.2 C*H(OCH.sub.3)CH.sub.3       444          C.sub.10 H.sub.21                                                                           H       H COOCH.sub.2 C*H(OC.sub.2 H.sub.5)CH.s                                         ub.3                                     445          C.sub.8 H.sub.17 O                                                                          H       H COOCH.sub.2 C*H(OC.sub.3 H.sub.7)CH.s                                         ub.3                                     446          C.sub.8 H.sub.17 O                                                                          H       H COO(CH.sub.2).sub.2 C*H(OC.sub.2                                              H.sub.5)CH.sub.3                         447          C.sub.8 H.sub.17 O                                                                          H       H COOC*H(CN)C.sub.2 H.sub.5                448          C.sub.8 H.sub.17 O                                                                          H       H COOCH.sub.2 C*H(CH.sub.3)CO.sub.2                                             CH.sub.3                                 449          C.sub.11 H.sub.23 O                                                                         H       H COOCH.sub.2 C*H(CH.sub.3)CO.sub.2                                             C.sub.2 H.sub.5                          450          C.sub.10 H.sub.21 O                                                                         H       H COOC*H(CH.sub.3)CH.sub.2 CO.sub.2                                             C.sub.2 H.sub.5                          451          C.sub.10 H.sub.21 O                                                                         H       H COOC*H(CH.sub.3)CH.sub.2 CO.sub.2                                             C.sub.4 H.sub.9                          452          C.sub.8 H.sub.17 O                                                                          H       H OCOC*H(CH.sub.3)C.sub.2 H.sub.5          453          C.sub.10 H.sub.21 O                                                                         H       H "                                        454          C.sub.8 H.sub.17 O                                                                          H       Cl                                                                              "                                        455          C.sub.8 H.sub.17 O                                                                          H       H OCOC*H(CH.sub.3)C.sub.3 H.sub.7          456          C.sub.8 H.sub.17 O                                                                          H       H OCO(CH.sub.2).sub.2 C*H(CH.sub.3)C.su                                         b.2 H.sub.5                              457          C.sub.10 H.sub. 21 O                                                                        H       H "                                        458          C.sub.12 H.sub.25 O                                                                         H       H "                                        459          C.sub.14 H.sub.29 O                                                                         H       H "                                        460          C.sub.10 H.sub.21 O                                                                         H       H                                                                                ##STR36##                               461          C.sub.8 H.sub.17 O                                                                          H       H OCOC*H(Cl)C*H(CH.sub.3)C.sub.2                                                H.sub.5                                  462          C.sub.10 H.sub.21 O                                                                         H       H "                                        463          C.sub.10 H.sub.21 O                                                                         H       H OCOC*H(Br)C*H(CH.sub.3)C.sub.2                                                H.sub.5                                  464          C.sub.12 H.sub.25 O                                                                         H       H "                                        465          C.sub.10 H.sub.21 O                                                                         H       H OCOC*H(Br)CH(CH.sub.3)CH.sub.3           466          C.sub.2 H.sub.5 C*H(CH.sub.3)CH.sub.2 OCO                                                   H       H COOCH.sub.2 C*H(CH.sub.3)C.sub.2                                              H.sub.5                                  467          C.sub.6 H.sub.13 C*H(CH.sub.3)OCO                                                           H       H COOC*H(CH.sub.3)C.sub.6 H.sub.13         468          C.sub.2 H.sub.5 C*H(CH.sub.3)OCO                                                            H       H "                                        469          C.sub.6 H.sub.13 C*H(CH.sub.3)O                                                             H       H OC*H(CH.sub.3)C.sub.6 H.sub.13           470          C.sub. 6 H.sub.13 C*H(CH.sub.3)O                                                            H       H CH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                                  471          C.sub.2 H.sub.5 C*H(CH.sub.3)O                                                              H       H CN                                       472          C.sub.6 H.sub.13 C*H(CH.sub.3)O                                                             H       H Br                                       473          C.sub.6 H.sub.13 C*H(CH.sub.3)O                                                             H       H COOC.sub.4 H.sub.9                       474          C.sub.6 H.sub.13 C*H(CH.sub.3)O                                                             H       H COOCH.sub.2 C*H(CH.sub.3)C.sub.2                                              H.sub.5                                  __________________________________________________________________________     ##STR37##                                                                    Example                                                                       Compound                                                                      No.         R.sub.1        X.sub.1 X.sub.2                                                                         R.sub.2                                  __________________________________________________________________________    475         C.sub.8 H.sub.17 O                                                                           H       H OCH.sub.2 C*H(CH.sub.3)C.sub.4                                                H.sub.9                                  476         C.sub.10 H.sub.21 O                                                                          H       H OCH.sub.2 C*H(OCH.sub.3)CH.sub.3         477         C.sub.12 H.sub.25 O                                                                          H       H OCH.sub.2 C*H(OC.sub.3 H.sub.7)CH.sub                                         .3                                       478         C.sub.9 H.sub. 19                                                                            H       H (CH.sub.2).sub.3 C*H(CH.sub.3)C.sub.2                                          H.sub.5                                 479         C.sub.11 H.sub.23                                                                            H       H OCOC*H(CH.sub.3)C.sub.2 H.sub.5          480         C.sub.2 H.sub.5 C*H(CH.sub.3)(CH.sub.2).sub.5                                                H       H OC.sub.8 H.sub.17                        481         C.sub.9 H.sub.19                                                                             H       H COOC*H(CH.sub.3)C.sub.6 H.sub.13         __________________________________________________________________________     ##STR38##                                                                    Example                                                                       Compound                                                                      No.      R.sub.1   X.sub.1                                                                         X.sub.2                                                                              X.sub.3                                                                         X.sub.4                                                                              Z      R.sub.2                           __________________________________________________________________________    482      C.sub.8 H.sub.17                                                                        H H      H H      COO    COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                          483      C.sub.9 H.sub.19                                                                        H H      H H      "      OCH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                          484      C.sub.11 H.sub.23                                                                       H H      Cl                                                                              H      "      OC*H(CH.sub.3)C.sub.3                                                         H.sub.7                           485      C.sub.12 H.sub.25                                                                       H H      H H      "      OCH.sub.2 C*H(OC.sub.2                                                        H.sub.5)CH.sub.3                  486      C.sub.9 H.sub.19                                                                        H H      H H      NCH    OC*H(CH.sub.3)C.sub.2                                                         H.sub.5                           487      C.sub.14 H.sub.29                                                                       H H      H H      NN     (CH.sub.2).sub.2 C*H(CH.sub.3)                                                C.sub.2 H.sub.5                   __________________________________________________________________________     ##STR39##                                                                    Example                                                                       Compound                                                                      No.      R.sub.1   X.sub.1                                                                         X.sub.2                                                                              X.sub.3                                                                         X.sub.4                                                                              Z      R.sub.2                           __________________________________________________________________________    488      C.sub.5 H.sub.11                                                                        H H      H H      COO    COOC*H(CH.sub.3)C.sub.5                                                       H.sub.11                          489      C.sub.10 H.sub.21                                                                       H H      H H      "      COO(CH.sub.2).sub.4 C*H(CH.sub                                                .3)C.sub.2 H.sub.5                490      C.sub.8 H.sub.17                                                                        H H      H H      "      OCH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                          491      C.sub.11 H.sub.23                                                                       H H      H H      "      OCOCH.sub.2 C*H(CH.sub.3)C.sub                                                .2 H.sub.5                        492      C.sub.7 H.sub.15                                                                        H H      H H      CHN    (CH.sub.2).sub.2 C*H(CH.sub.3)                                                C.sub.2 H.sub.5                   __________________________________________________________________________     ##STR40##                                                                    Example                                                                       Compound                                                                      No.      R.sub.1   X.sub.1                                                                         X.sub.2                                                                              X.sub.3                                                                         X.sub.4                                                                             Z       R.sub.2                           __________________________________________________________________________    493      C.sub.3 H.sub.7                                                                         H H      H H     COO     COO(CH.sub.2).sub.3 C*H(CH.sub                                                .3)C.sub.2 H.sub. 5               494      C.sub.10 H.sub.21                                                                       H H      Cl                                                                              H     "       COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                          495      C.sub.5 H.sub.11                                                                        H H      H H     NN      OCH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                          496      C.sub.7 H.sub.15                                                                        H H      H H     N(O)N   OC*H(CH.sub.3)C.sub.7             __________________________________________________________________________                                                H.sub.15                           ##STR41##                                                                    Example                                                                       Compound                                                                      No.      R.sub.1   X.sub.1                                                                         X.sub.2                                                                              X.sub.3                                                                         X.sub.4                                                                              Z     R.sub.2                            __________________________________________________________________________    497      C.sub.7 H.sub.15                                                                        H H      H H      COO   COOCH.sub.2 C*H(CH.sub.3)C.sub.                                               2 H.sub.5                          498      C.sub.10 H.sub.21                                                                       H H      Cl                                                                              H      "     COO(CH.sub.2).sub.2                                                           C*H(CH.sub.3)C.sub.2 H.sub.5       499      C.sub.12 H.sub.25                                                                       H H      H H      "     COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                           500      C.sub.8 H.sub.17                                                                        H H      H H      "     OC*H(CH.sub.3)C.sub.2 H.sub.5      501      C.sub.10 H.sub.21                                                                       H H      H H      "     OCOCH.sub.2 C*H(CH.sub.3)C.sub.                                               2 H.sub.5                          502      C.sub.11 H.sub.23                                                                       H F      H H      "     CH.sub.2 C*H(CH.sub.3)C.sub.2                                                 H.sub.5                            __________________________________________________________________________     ##STR42##                                                                    Example                                                                       Compound                                                                      No.      R.sub.1   X.sub.1                                                                         X.sub.2                                                                              X.sub.3                                                                         X.sub.4  Z     R.sub.2                          __________________________________________________________________________    503      C.sub.4 H.sub.9                                                                         H H      H F        COO   COOCH.sub.2                                                                   C*H(CH.sub.3)C.sub.2                                                          H.sub.5                          504      C.sub.7 H.sub.15                                                                        H H      Cl                                                                              H        "     COOC*H(CH.sub.3)C.sub.6                                                       H.sub.13                         505      C.sub.10 H.sub.21                                                                       H H      H H        "     "                                506      C.sub.8 H.sub.17                                                                        H H      H H        "     O(CH.sub.2).sub.4 C*H(CH.sub.                                                 3)C.sub.2 H.sub.5                507      C.sub.11 H.sub.23                                                                       H H      H H        "     OCH.sub.2 C*H(OC.sub.4                                                        H.sub.9)CH.sub.3                 508      C.sub.14 H.sub.29                                                                       H H      H C.sub.2 H.sub.5                                                                        "     CH.sub.2 C*H(CH.sub.3)C.sub.2                                                  H.sub.5                         __________________________________________________________________________

EXAMPLES

Now, the present invention will be described in detail in accordancewith examples, but needless to say, the purport and the applied scope ofthe present invention should not be limited to these examples.

In tables given below, the symbol C represents a crystal phase, SC*represents a chiral smectic C phase, SA represents a smectic A phase, Chrepresents a cholesteric (chiral nematic) phase, I represents anisotropic liquid, and SX represents an unknown smectic phase. Further,the symbol "." of each phase and a numeral on its right side indicate aphase transition temperature from this phase to a phase on its rightside, and the symbol "-" means that the compound does not show itsphase. Furthermore, a value in each pair of round parentheses representsa monotropic phase transition temperature, and the symbol "*" representsan asymmetric carbon atom.

EXAMPLE 1 Preparation of (R)--6-benzyloxynaphthalene-2-carboxylic acid1'-methylheptyl ester

In 500 ml of benzene, 65 g of 6-benzyloxynaphthalene-2-carboxylic acidwas heated at reflux together with 50 g of oxalyl chloride for a periodof 4 hours, and afterward the excessive oxalyl chloride and benzene weredistilled out under reduced pressure in order to obtain an acidchloride. This acid chloride was then dissolved in 100 ml of benzene,and to the resulting solution was added a solution in which 30 g of(R)--2-octanol was dissolved in 30 ml of pyridine. Then, the mixedsolution was allowed to stand at room temperature for 8 hours. Aprecipitated pyridine hydrochloride was filtered out, and an organiclayer was then washed with a 2N hydrochloric acid solution and a 2Naqueous sodium hydroxide solution. Further, water washing was thencarried out until the solution had become neutral. The organic layer wasseparated and then dried with anhydrous magnesium sulfate, and the usedbenzene was distilled out under reduced pressure. The resulting residuewas recrystallized out of ethanol in order to prepare 80 g of thedesired (R)--6-benzyloxynaphthalene-2-carboxylic acid 1'-methylheptylester.

A phase transition temperature of this compound is set forth in Table 3.

Analytical values of elements constituting this compound are closely inaccord with theoretical values, as follows:

    ______________________________________                                        Theoretical Value (as C.sub.26 H.sub.30 O.sub.3)                                                  Analytical Value                                          ______________________________________                                        C           79.96%      79.89%                                                H            7.74%       7.70%                                                ______________________________________                                    

EXAMPLE 2 TO 8

The same procedure as in Example 1 was repeated with the exception that(R)-2-octanol was replaced with various optically active alcohols, inorder to prepare various optically active6-benzyloxynaphthalene-2-carboxylic acid alkyl esters. Their phasetransition temperatures which are physical values are set forth in Table3.

EXAMPLE 9 Preparation of(R)-6-(4'-decyloxyphenylcarbonyloxy)-2-naphthalenecarboxylic acid1"-methylheptyl ester

(i) First, 30 g of (R)--6-benzyloxynaphthalene-2-carboxylic acid1'-methylheptyl ester prepared in Example 1 was dissolved in 200 ml ofethanol, and hydrogenation was then carried out at 40° C. underatmospheric pressure in the presence of 4 g of a 5% palladium/carboncomposite. The latter was then filtered out, and the used solvent wasdistilled out under reduced pressure in order to prepare 23 g of abenzyl group-free product having a melting point of 67° to 68° C.

(ii) Next, 4.0 g of (R)--6-hydroxynaphthalene-2-carboxylic acid 1-methylheptyl ester which was the product of the preceding paragraph(i), 3.7 g of 4-decyloxybenzoic acid, 2.6 g ofN,N'-dicyclohexylcarbodiimide and 10 mg of 4-pyrrolidinopyridine weredissolved in 50 ml of chloroform, and the resulting mixture was thenallowed to stand at room temperature for 8 hours. A secondarily producedN,N'-dicyclohexyl urea was filtered out, and an organic layer was thenwashed with a 2N hydrochloric acid solution and a 2N aqueous sodiumhydroxide solution, followed by water washing. The organic layer wasthen dried with anhydrous magnesium sulfate, and the used solvent wasdistilled out to prepare a crude product. The latter was then purifiedby the use of a silica gel column chromatography utilizing benzene as aneluent. Further, recrystallization was accomplished out of ethanol toprepare 5.0 g of the desired(R)--6-(4'-decyloxyphenylcarbonyloxy-2-naphthalenecarboxylic acid1"-methylheptyl ester in the state of a colorless needle crystal. Theyield was 67%. A phase transition temperature of the thus preparedcompound is set forth in Table 3. Analytical values of elementsconstituting this compound are closely in accord with theoreticalvalues, as follows:

    ______________________________________                                        Theoretical Value (as C.sub.36 H.sub.48 O.sub.5)                                                  Analytical Value                                          ______________________________________                                        C           77.11%      77.25%                                                H            8.63%       8.59%                                                ______________________________________                                    

When measured at a 10° C lower temperature than an SC*-SA phasetransition temperature, a value of a spontaneous polarization (Ps) was87 nC/cm².

EXAMPLES 10 TO 19

The same procedure as in the process (ii) in Example 9 was repeated withthe exception that 4-decyloxybenzoic acid was replaced with various4-alkyloxybenzoic acids, 4-alkylbenzoic acids or4-alkyloxy-3-halogenobenzoic acids, in order to thereby prepare variousester compounds. Their phase transition temperatures which are physicalvalues are all set forth in Table 3.

EXAMPLES 20 TO ↓

Various ester compounds were prepared in a manner similar to that ofExample 9 (ii) from various optically active6-hydroxynaphthalene-2-carboxylic acid alkyl esters or various opticallyactive 6-hydroxy-5-halogenonaphthalene2-carboxylic acid alkyl estersprepared in a manner similar to that of Example 9 (i) and various4-alkoxybenzoic acids, 4-alkoxy-3-halogenobenzoic acids or opticallyactive 4-alkoxybenzoic acids. Their phase transition temperatures whichare physical values are set forth in Table 3.

EXAMPLE 76 Preparation of(s)--6-(2'-methylbutyloxy)--2-naphthyl-4"-decyloxybenzoic acid ester

To 50 ml of methylene chloride were added 1.0 g of 4-decyloxybenzoicacid, 750 mg of (s)--6-(2 -methylbutyloxy)-2-naphthol, 700 mg ofN,N'-dicyclohexylcarbodiimide and 20 mg of 4-pyrrolidinopyridine, andthe resulting mixture was then allowed to stand at room temperature for4 hours. Secondarily produced N,N'-dicyclohexyl urea was filtered out,and an organic layer was then washed with a 5% hydrochloric acidsolution, a 5% aqueous sodium hydroxide solution and water in thisorder, followed by drying with anhydrous magnesium sulfate. Methylenechloride was then distilled out, and the resulting residue was purifiedby the use of a silica gel column chromatography utilizing benzene as aneluent. The thus obtained crystal was recrystallized twice out ofethanol to prepare 750 mg of the desired(s)-6-(2'-methylbutyloxy)-2-naphthyl-4"-decyloxybenzoic acid ester inthe state of a colorless needle crystal. The yield was 47%. A phasetransition temperature of the thus prepared compound is set forth inTable 3. Analytical values of elements constituting this compound areclosely in accord with theoretical values, as follows:

    ______________________________________                                        Theoretical Value (as C.sub.32 H.sub.42 O.sub.4)                                                  Analytical Value                                          ______________________________________                                        C           78.33%      78.41%                                                H            8.63%       8.72%                                                ______________________________________                                    

When measured at a 10° C. lower temperature than an SC*-SA transitiontemperature, a value of a spontaneous polarization (Ps) was 2 nC/cm².

EXAMPLES 77 TO 86

The same procedure as in Example 76 was repeated with the exception that4-decyloxybenzoic acid was replaced with various 4-alkoxybenzoic acidsor 4-alkylbenzoic acids in order to prepare optically active variousester compounds. Their phase transition temperatures which are physicalvalues are set forth in Table 3.

EXAMPLES 87 TO 110

Following the same procedure as in Example 76, various optically active6-alkyloxy-2-naphthol or optically active 6-alkoxyalkyloxy-2-naphtholswere reacted with 4-alkoxybenzoic acids, and various6-alkoxy-2-naphthols were reacted with optically active 4-alkoxybenzoicacids, in order to prepare various optically active esters. Their phasetransition temperatures which are physical values are set forth in Table3.

EXAMPLE 111 Preparation of(s)--4'-(2"-methylbutyloxy)phenyl-6-octyloxynaphthalene-2-carboxylicacid ester

In 50 ml of methylene chloride were dissolved 1.8 g of6-octyloxynaphthalene-2-carboxylic acid, 1.1 g of(s)-4-(2'-methylbutyloxy)phenol, 1.2 g of N,N'-dicyclohexylcarbodiimideand 50 mg of 4-pyrrolidinopyridine, and the resulting mixture was thenallowed to stand at room temperature for 15 hours. Secondarily producedN,N'-dicyclohexyl urea was filtered out, and an organic layer was thenwashed with a 5% hydrochloric acid solution, a 5% aqueous sodiumhydroxide solution and water in this order, followed by drying withanhydrous magnesium sulfate. Methylene chloride was distilled out, andthe resulting residue was then purified by the use of a silica gelcolumn chromatography utilizing benzene as an eluent. The thus obtainedcrystal was recrystallized twice out of ethanol to prepare the desired(s)-4'-2"-methylbutyloxy)phenyl-6-octyloxynaphthalene-2-carboxylic acidester in the state of a colorless needle crystal. The yield was 59%.

A phase transition temperature of the thus prepared compound is setforth in Table 3. Analytical values of elements constituting thiscompound are closely in accord with theoretical values, as follows:

    ______________________________________                                        Theoretical Value (as C.sub.30 H.sub.38 O.sub.4)                                                  Analytical Value                                          ______________________________________                                        C           77.89%      77.95%                                                H            8.28%       8.20%                                                ______________________________________                                    

EXAMPLES 112 AND 113

The same procedure as in Example 111 was repeated with the exceptionthat 4-octyloxybenzoic acid was replaced with various 4-alkoxybenzoicacids in order to prepare ester compounds. Their phase transitiontemperatures which are physical values are set forth in Table 3.

EXAMPLES 114 TO 131

Following the same procedure as in Example 111, optically active4-alkoxyphenols or optically active 4-alkylphenols were reacted withvarious 6-alkoxynaphthalene-2-carboxylic acid, or various4-alkoxyphenols were reacted with various optically active6-alkoxynaphthalene-2-carboxylic acids or 4-halogenophenols, or4-cyanophenol or 3-halogeno-4-cyanophenols were reacted with opticallyactive 6-alkoxynaphthalene-2-carboxylic acids, in order to preparevarious esters. Their phase transition temperatures which are physicalvalues are set forth in Table 3.

EXAMPLES 132

Preparation of (s)-4-(6'-octyloxy-2'-naphthoyloxy)-benzoic acid2"-methylbutyl ester

In 30 ml of methylene chloride were dissolved 700 mg of(s)-4-hydroxybenzoic acid 2'-methylbutyl ester, 1.0 g of6-octyloxynaphthalene-2-carboxylic acid, 700 mg ofN,N'-dicyclohexylcarbodiimide and 20 mg of 4-pyrrolidinopyridine, andthe resulting mixture was then allowed to stand at room temperature for10 hours. Secondarily produced N,N'-dicyclohexyl urea was filtered out,and an organic layer was then washed with a 5% hydrochloric acidsolution, a 5% aqueous sodium hydroxide solution and water in thisorder, followed by drying with anhydrous magnesium sulfate. Methylenechloride was distilled out, and the resulting residue was then purifiedby the use of a silica gel column chromatography utilizing benzene as aneluent. The thus obtained crystal was recrystallized out of ethanol toprepare 1.1 g of the desired (s)-4-(6'-octyloxy-2'-naphthoyloxy)benzoicacid 2"-methylbutyl ester in the state of a colorless needle crystal.The yield was 67%.

A phase transition temperature of the thus prepared compound is setforth in Table 3. Analytical values of elements constituting thiscompound are closely in accord with theoretical values, as follows:

    ______________________________________                                        Theoretical value (as C.sub.31 H.sub.38 O.sub.5)                                                  Analytical Value                                          ______________________________________                                        C           75.89%      75.75%                                                H            7.81%       7.79%                                                ______________________________________                                    

EXAMPLES 133 TO 135

The same procedure as in Example 132 was repeated with the exceptionthat 6-octyloxynaphthalene-2-carboxylic acid was replaced with various6-alkyloxynaphthalene-2-carboxylic acids in order to prepare variousester compounds. Their phase transition temperatures which are physicalvalues are set forth in Table 3.

EXAMPLES 136 TO 151

Following the same procedure as in Example 132, various optically active4-hydroxybenzoic acid alkyl esters were reacted with various6-alkoxynaphthalene-2-carboxylic acids or6-alkoxyalkyloxynaphthalene-2-carboxylic acids in order to preparevarious ester compound. Their phase transition temperatures which arephysical values are set forth in Table 3.

                                      TABLE 3                                     __________________________________________________________________________     Num-pleExam-                                                                      ##STR43##                                                                ber Wherein A represents                                                                            Wherein B represents                                                                              X Phase transition temperature                                                  (°C.)                      __________________________________________________________________________                                                C   SC* SA   Ch  I                 1                                                                                 ##STR44##                                                                                       ##STR45##          H • 69.5                                                                      --  --   --  •           2  "                                                                                                ##STR46##          H • 87.0                                                                      --  --   --  •           3  "                                                                                                ##STR47##          H • 60.5                                                                      --  --   --  •           4  "                                                                                                ##STR48##          H • 78.5                                                                      --  --   --  •           5  "                                                                                                ##STR49##          H • 65.0                                                                      --  --   --  •           6  "                                                                                                ##STR50##          H • 51.5                                                                      --  --   --  •           7                                                                                 ##STR51##                                                                                       ##STR52##          H • 58.4                                                                      --  --   --  •           8  "                                                                                                ##STR53##          H <10                                9                                                                                 ##STR54##                                                                                       ##STR55##          H • 46.5                                                                      (• 41.5)                                                                    • 64.6                                                                       --  •          10                                                                                 ##STR56##        "                   H • 97.0                                                                      --  --   --  •          11                                                                                 ##STR57##        "                   H • 53.8                                                                      --  • 66.7                                                                       --  •          12                                                                                 ##STR58##        "                   H • 63.0                                                                      (• 30.0)                                                                    • 63.5                                                                       --  •          13                                                                                 ##STR59##                                                                                       ##STR60##          H • 59.7                                                                      (• 42.5)                                                                    • 62.4                                                                       --  •          14                                                                                 ##STR61##        "                   H • 50.5                                                                      (• 49.7)                                                                    • 63.0                                                                       --  •          15                                                                                 ##STR62##        "                   H • 57.3                                                                      (• 56.0)                                                                    • 62.1                                                                       --  •          16                                                                                 ##STR63##        "                   H • 54.5                                                                      (• 50.5)                                                                    • 62.1                                                                       --  •          17                                                                                 ##STR64##        "                   H • 39.2                                                                      (• 37.6)                                                                    • 53.1                                                                       --  •          18                                                                                 ##STR65##        "                   H • 47.5                                                                      (• 46.0)                                                                    • 52.2                                                                       --  •          19                                                                                 ##STR66##        "                   H • 47.6                                                                      --  --   --  •          20                                                                                 ##STR67##                                                                                       ##STR68##          H • 119.4                                                                     --  --   --  •          21                                                                                 ##STR69##        "                   H • 69.0                                                                      --  • 76.5                                                                       --  •          22                                                                                 ##STR70##        "                   H • 76.6                                                                      --  (• 74.4)                                                                     --  •          23                                                                                 ##STR71##        "                   H • 54.0                                                                      • 56.0                                                                      • 74.4                                                                       --  •          24                                                                                 ##STR72##        "                   H •  63.0                                                                     (• 51.5)                                                                    • 71.0                                                                       --  •          25                                                                                 ##STR73##        "                   H • 60.7                                                                      (• 53.5)                                                                    • 71.5                                                                       --  •          26                                                                                 ##STR74##        "                   H • 50.1                                                                      (• 46.8)                                                                    • 60.7                                                                       --  •          27                                                                                 ##STR75##                                                                                       ##STR76##          H • 94.5                                                                      --  --   --  •          28                                                                                 ##STR77##        "                   H • 69.1                                                                      (• 49.6)                                                                    • 85.5                                                                       --  •          29                                                                                 ##STR78##        "                   H • 57.0                                                                      • 55.5                                                                      • 86.8                                                                       --  •          30                                                                                 ##STR79##        "                   H • 59.1                                                                      (• 54.5)                                                                    • 86.7                                                                       --  •          31                                                                                 ##STR80##        "                   H • 55.0                                                                      (• 53.0)                                                                    • 86.6                                                                       --  •          32                                                                                 ##STR81##        "                   H • 61.5                                                                      (• 54.5)                                                                    • 85.1                                                                       --  •          33                                                                                 ##STR82##        "                   H • 56.5                                                                      (• 55.0)                                                                    • 84.5                                                                       --  •          34                                                                                 ##STR83##                                                                                       ##STR84##          H • 55.0                                                                      (• 45.2)                                                                    • 77.7                                                                       --  •          35                                                                                 ##STR85##        "                   H • 50.4                                                                      (• 40.5)                                                                    • 73.4                                                                       --  •          36                                                                                 ##STR86##                                                                                       ##STR87##          H • 99.5                                                                      --  (• 83.9)                                                                     • 100.9                                                                     •          37                                                                                 ##STR88##        "                   H • 81.7                                                                      --  • 98.7                                                                       • 105.7                                                                     •          38                                                                                 ##STR89##        "                   H • 70.8                                                                      (• 54.6)                                                                     • 100.7                                                                     • 101.9                                                                     •          39                                                                                 ##STR90##        "                   H • 62.1                                                                      (• 59.0)                                                                     • 102.8                                                                     --  •          40                                                                                 ##STR91##        "                   H • 60.1                                                                      • 66.9                                                                       • 102.9                                                                     --  •          41                                                                                 ##STR92##        "                   H • 58.4                                                                      • 66.0                                                                       • 104.0                                                                     --  •          42                                                                                 ##STR93##                                                                                       ##STR94##          H • 70.2                                                                      • 73.7                                                                       • 103.8                                                                     --  •          43                                                                                 ##STR95##        "                   H • 77.2                                                                      (• 71.3)                                                                     • 104.0                                                                     --  •          44                                                                                 ##STR96##        "                   H • 67.6                                                                      • 73.5                                                                       • 103.4                                                                     --  •          45                                                                                 ##STR97##        "                   H • 59.8                                                                      • 63.6                                                                       • 102.1                                                                     --  •          46                                                                                 ##STR98##        "                   H • 58.6                                                                      • 66.4                                                                       • 102.1                                                                     --  •          47                                                                                 ##STR99##        "                   H • 65.6                                                                      • 58.1                                                                       • 100.1                                                                     --  •          48                                                                                 ##STR100##       "                   H • 59.5                                                                      • 64.0                                                                      • 99.7                                                                       --  •          49                                                                                 ##STR101##       "                   H • 114.5                                                                     --  --   --  •          50                                                                                 ##STR102##                                                                                      ##STR103##         H • 73.0                                                                      (• 38.8)                                                                    • 92.8                                                                       --  •          51                                                                                 ##STR104##       "                   H • 74.3                                                                      (• 50.8)                                                                    • 92.5                                                                       --  •          52                                                                                 ##STR105##       "                   H • 64.0                                                                      (• 57.4)                                                                    • 91.8                                                                       --  •          53                                                                                 ##STR106##       "                   H • 63.9                                                                      (• 57.5)                                                                    • 94.5                                                                       --  •          54                                                                                 ##STR107##       "                   H • 57.4                                                                      • 58.1                                                                      • 89.0                                                                       --  •          55                                                                                 ##STR108##       "                   H • 103.1                                                                     --  --   --  •          56                                                                                 ##STR109##                                                                                      ##STR110##         H • 73.7                                                                      --  (• 66.2)                                                                     --  •          57                                                                                 ##STR111##       "                   H • 52.8                                                                      --  • 70.5                                                                       --  •          58                                                                                 ##STR112##       "                   H • 57.5                                                                      --  --   --  •          59                                                                                 ##STR113##                                                                                      ##STR114##         H • 56.3                                                                      • 73.0                                                                       • 103.3                                                                     --  •          60                                                                                 ##STR115##       "                   H • 68.8                                                                      (• 67.0)                                                                    • 90.3                                                                       --  •          61                                                                                 ##STR116##                                                                                      ##STR117##         H • 72.0                                                                      (• 68.5)                                                                    • 91.0                                                                       --  •          62                                                                                 ##STR118##       "                   H • 75.0                                                                      (• 74.3)                                                                    • 88.0                                                                       --  •          63                                                                                 ##STR119##                                                                                      ##STR120##         H • 49.5                                                                      --  --   --  •          64                                                                                 ##STR121##                                                                                      ##STR122##         H • 66.6                                                                      •                                                                            • 100.5                                                                     --  •          65                                                                                 ##STR123##       "                   H • 52.5                                                                      • 64.0                                                                      • 99.2                                                                       --  •          66                                                                                 ##STR124##       "                   H • 51.6                                                                      • 73.0                                                                      • 99.1                                                                       --  •          67                                                                                 ##STR125##       "                   H • 54.2                                                                      • 78.5                                                                      • 99.7                                                                       --  •          68                                                                                 ##STR126##       "                   H • 64.3                                                                      • 80.5                                                                       • 101.3                                                                     --  •          69                                                                                 ##STR127##       "                   H • 64.9                                                                      • 80.5                                                                      • 98.6                                                                       --  •          70                                                                                 ##STR128##       "                   H • 58.0                                                                      • 82.9                                                                      • 98.5                                                                       --  •          71                                                                                 ##STR129##                                                                                      ##STR130##         H • 67.7                                                                      • 79.5                                                                      • 98.8                                                                       --  •          72                                                                                 ##STR131##       "                   H • 58.7                                                                      • 75.9                                                                      • 88.9                                                                       --  •          73                                                                                 ##STR132##                                                                                      ##STR133##         H • 54.5                                                                      • 90.0                                                                       • 100.3                                                                     --  •          74                                                                                 ##STR134##                                                                                      ##STR135##         Cl                                                                              • 47.5                                                                      --  • 59.5                                                                       • 68.9                                                                      •          75                                                                                 ##STR136##       "                   Cl                                                                              • 48.2                                                                      --  • 72.1                                                                       --  •          76                                                                                 ##STR137##                                                                                      ##STR138##         H • 64.5                                                                      • 77.1                                                                      • 85.5                                                                       • 98.7                                                                      •          77                                                                                 ##STR139##       "                   H • 85.1                                                                      --  --   • 100.7                                                                     •          78                                                                                 ##STR140##                                                                                      ##STR141##         H • 77.2                                                                      (• 71.2)                                                                    --   • 102.8                                                                     •          79                                                                                 ##STR142##       "                   H • 62.0                                                                      • 76.1                                                                      • 76.9                                                                       • 98.0                                                                      •          80                                                                                 ##STR143##       "                   H • 68.0                                                                      • 79.2                                                                      • 89.0                                                                       • 96.5                                                                      •          81                                                                                 ##STR144##       "                   H • 67.2                                                                      • 76.9                                                                      • 91.6                                                                       • 97.0                                                                      •          82                                                                                 ##STR145##       "                   H • 74.3                                                                      • 78.5                                                                      • 92.7                                                                       • 95.5                                                                      •          83                                                                                 ##STR146##       "                   H • 73.3                                                                      • 75.3                                                                      • 93.7                                                                       • 95.0                                                                      •          84                                                                                 ##STR147##       "                   H • 79.1                                                                      (• 73.0)                                                                    • 93.4                                                                       • 94.0                                                                      •          85                                                                                 ##STR148##       "                   H • 80.3                                                                      --  • 93.0                                                                       --  •          86                                                                                 ##STR149##       "                   H • 71.7                                                                      --  --   (•                                                                          •          87                                                                                 ##STR150##                                                                                      ##STR151##         H • 82.3                                                                      --  --   • 117.1                                                                     •          88                                                                                 ##STR152##       "                   H • 71.2                                                                      • 72.6                                                                      --   • 114.6                                                                     •          89                                                                                 ##STR153##       "                   H • 67.7                                                                      • 89.0                                                                      --   • 110.8                                                                     •          90                                                                                 ##STR154##       "                   H • 67.0                                                                      • 94.3                                                                      • 95.2                                                                       • 106.0                                                                     •          91                                                                                 ##STR155##       "                   H • 73.1                                                                      • 94.7                                                                      • 99.4                                                                       • 103.3                                                                     •          92                                                                                 ##STR156##       "                   H • 79.0                                                                      • 92.7                                                                      • 99.1                                                                       • 101.0                                                                     •          93                                                                                 ##STR157##       "                   H • 80.3                                                                      --  --   • 86.4                                                                      •          94                                                                                 ##STR158##                                                                                      ##STR159##         H • 57.7                                                                      --  --   (•                                                                          •          95                                                                                 ##STR160##       "                   H • 41.5                                                                      • 47.8                                                                      --   • 59.4                                                                      •          96                                                                                 ##STR161##       "                   H • 60.0                                                                      (• 49.1)                                                                    --   (•                                                                          •          97                                                                                 ##STR162##       "                   H • 65.2                                                                      --  --   --  •          98                                                                                 ##STR163##       "                   H • 58.0                                                                      (• 50.0)                                                                    • 58.9                                                                       • 61.0                                                                      •          99                                                                                 ##STR164##       "                   H • 57.3                                                                      (• 56.2)                                                                    • 61.7                                                                       • 62.0                                                                      •          100                                                                                ##STR165##       "                   H • 48.5                                                                      • 53.0                                                                      • 63.5                                                                       --  •          101                                                                                ##STR166##       "                   H • 53.5                                                                      • 56.8                                                                      • 65.1                                                                       --  •          102                                                                                ##STR167##                                                                                      ##STR168##         H • 52.5                                                                      • 54.7                                                                      --   • 59.5                                                                      •          103                                                                                ##STR169##                                                                                      ##STR170##         H • 61.7                                                                      (• 50.5)                                                                    --   • 62.1                                                                      •          104                                                                                ##STR171##       "                   H • 57.3                                                                      (• 54.7)                                                                    • 57.2                                                                       • 60.3                                                                      •          105                                                                                ##STR172##                                                                                      ##STR173##         H • 62.2                                                                      --  • 65.8                                                                       • 80.1                                                                      •          106                                                                                ##STR174##       "                   H • 50.5                                                                      • 68.1                                                                      • 76.5                                                                       • 78.0                                                                      •          107                                                                                ##STR175##                                                                                      ##STR176##         H • 64.6                                                                      • 56.5                                                                      • 65.5                                                                       • 72.8                                                                      •          108                                                                                ##STR177##       OC.sub.10 H.sub.21  H • 76.3                                                                      --  --   • 98.4                                                                      •          109                                                                                ##STR178##       OC.sub.10 H.sub.21  H • 43.1                                                                      --  --   • 54.3                                                                      •          110                                                                                ##STR179##       OC.sub.10 H.sub.21  H • 61.5                                                                      • 74.1                                                                      --   • 113.1                                                                     •          111 C.sub.8 H.sub.17 O                                                                               ##STR180##         H • 100.6                                                                     --   • 108.3                                                                     • 108.7                                                                     •          112 C.sub.6 H.sub.13 O                                                                              "                   H • 101.6                                                                     --  (• 98.8)                                                                     • 108.9                                                                     •          113 C.sub.10 H.sub.21 O                                                                             "                   H • 103.0                                                                     --   • 109.5                                                                     --  •          114 C.sub.6 H.sub.13 O                                                                               ##STR181##         H • 74.5                                                                      • 80.4                                                                      •                                                                            • 117.8                                                                     •          115 C.sub.8 H.sub.17 O                                                                              "                   H • 73.6                                                                      • 84.0                                                                       • 111.1                                                                     • 116.8                                                                     •          116 C.sub.10 H.sub.21 O                                                                             "                   H • 60.6                                                                      • 93.6                                                                       • 114.9                                                                     --  •          117 C.sub.12 H.sub.25 O                                                                             "                   H • 55.5                                                                      • 96.1                                                                       • 114.1                                                                     --  •          118 C.sub.14 H.sub.29 O                                                                             "                   H • 62.0                                                                      • 94.8                                                                       • 110.8                                                                     --  •          119 C.sub.4 H.sub.9 O                                                                                ##STR182##         H • 37.7                                                                      --  --   • 41.0                                                                      •          120 C.sub.7 H.sub.15 O                                                                              "                   H • 42.5                                                                      --  --   (•                                                                          •                                                      C   SA     Ch  I                  121                                                                                ##STR183##                                                                                      ##STR184##         H • 84.6                                                                      --     • 96.9                                                                      •            122 "                                                                                                ##STR185##         H • 81.5                                                                      --     • 96.0                                                                      •            123 "                                                                                                ##STR186##         H • 79.9                                                                      --     • 94.2                                                                      •            124 "                                                                                                ##STR187##         H • 79.6                                                                      --     • 91.0                                                                      •            125                                                                                ##STR188##                                                                                      ##STR189##         H • 87.6                                                                      • 98.1                                                                         • 113.0                                                                     •            126 "                                                                                                ##STR190##         H • 71.8                                                                      • 84.5                                                                         • 110.7                                                                     •            127 "                                                                                                ##STR191##         H • 73.7                                                                      • 87.9                                                                         • 108.8                                                                     •            128 "                                                                                                ##STR192##         H • 71.4                                                                      • 78.4                                                                         • 104.7                                                                     •            129                                                                                ##STR193##                                                                                      ##STR194##         H • 52.0                                                                      --     --  •            130 "                                                                                                ##STR195##         H • 35.7                                                                      --     --  •            131 "                                                                                                ##STR196##         H <10                                                                           C   SC*    SA  I                  132 C.sub.8 H.sub.17 O                                                                               ##STR197##         H • 69.4                                                                      --     • 103.9                                                                     •            133 C.sub.10 H.sub.21 O                                                                             "                   H • 85.2                                                                      --     • 103.6                                                                     •            134 C.sub.12 H.sub.25 O                                                                             "                   H • 63.4                                                                      --     • 101.4                                                                     •            135 C.sub.14 H.sub.29 O                                                                             "                   H • 62.3                                                                      --     • 99.4                                                                      •            136 C.sub.10 H.sub.21 O                                                                              ##STR198##         H • 52.0                                                                      --     • 73.2                                                                      •            137 C.sub.12 H.sub.25 O                                                                             "                   H • 57.3                                                                      --     • 71.0                                                                      •            138 C.sub.6 H.sub.13 O                                                                               ##STR199##         H • 79.5                                                                      --     • 101.4                                                                     •            139 C.sub.8 H.sub.17 O                                                                              "                   H • 82.8                                                                      --     • 100.9                                                                     •            140 C.sub.10 H.sub.21 O                                                                             "                   H • 74.7                                                                      --     • 100.2                                                                     •            141 C.sub.12 H.sub.25 O                                                                             "                   H • 59.5                                                                      • 68.0                                                                         • 102.6                                                                     •            142 C.sub.14 H.sub.29 O                                                                             "                   H • 68.5                                                                      (• 64.9)                                                                       • 95.5                                                                      •            143 C.sub.16 H.sub.33 O                                                                             "                   H • 55.8                                                                      • 60.3                                                                         • 88.0                                                                      •            144 C.sub.12 H.sub.25 O                                                                              ##STR200##         H • 62.3                                                                      --     • 73.5                                                                      •            145 C.sub.4 H.sub.9 O(CH.sub.2).sub.2 O                                                             "                   H • 47.0                                                                      --     • 52.5                                                                      •            146 C.sub.8 H.sub.17 O                                                                               ##STR201##         H • 55.5                                                                      --     • 68.7                                                                      •            147 C.sub.9 H.sub.19 O                                                                              "                   H • 61.7                                                                      --     • 67.5                                                                      •            148 C.sub.10 H.sub.21 O                                                                             "                   H • 57.7                                                                      --     • 67.7                                                                      •            149 C.sub.7 H.sub.15 O                                                                               ##STR202##         H • 60.3                                                                      --     • 65.3                                                                      •            150 C.sub.9 H.sub.19 O                                                                              "                   H • 63.7                                                                      --     • 64.8                                                                      •            151 C.sub.11 H.sub.23 O                                                                             "                   H • 54.8                                                                      --     • 64.9                                                                      •            __________________________________________________________________________

EXAMPLE 152 Preparation of(s)-6-(4"-octyloxybiphenyl-4'-carbonyl)-2-naphthalenecarboxylic acid2'"-methylbutyl ester

In 300 ml of benzene, 5.0 g of 4'-octyloxybiphenyl-4-carboxylic acid and20 ml of thionyl chloride were heated at reflux temperature for 5 hours,and afterward the excessive thionyl chloride and benzene were distilledout under reduced pressure. To carboxylic acid chloride of the residualwere added 4.0 of (s)-6-hydroxynaphthalene-2-carboxylic acid2"-methylbutyl ester, 30 ml of pyridine and 300 ml of benzene, and theresulting mixture was heated at reflux for 5 hours. After the mixturehad been cooled to room temperature, pyridine hydrochloride was filteredout, and an obtained filtrate was then washed with water, a 10%hydrochloric acid solution, a saturated aqueous NaHCO₃ solution andwater in this order, followed by drying with anhydrous magnesiumsulfate. After the removal of benzene by distillation, the resultingresidue was then separated and purified by the sue of a silica gelcolumn chromatography utilizing benzene as an eluent. The thus obtainedcrystal was recrystallized out of ethanol-ethyl acetate to prepare 4.5 gof the desired (s)-6-(4"-octyloxybiphenyl-4'-carbonyloxy)-2-naphthalenecarboxylic acid2"-methylbutyl ester in the state of a colorless crystal. The yield was52%. A phase transition temperature of the thus prepared compound is setforth in Table 4. Analytical values of elements constituting thiscompound are closely in accord with theoretical values, as follows:

    ______________________________________                                        Theoretical Value (as C.sub.37 H.sub.42 O.sub.5)                                                  Analytical Value                                          ______________________________________                                        C           78.41%      78.50%                                                H            7.47%       7.43%                                                ______________________________________                                    

When measured at a 10° C. lower temperature than an SC*-SA transitiontemperature, a value of a spontaneous polarization (Ps) was 5 nC/cm².

EXAMPLES 153 TO 164

The same procedure as in Example 152 was repeated with the exceptionthat 4'-octyloxybiphenyl-4-carboxylic acid was replaced with various4'-alkyloxybiphenyl-4-carboxylic acids, 4'-alkylbiphenyl-4-carboxylicacids or 3'-halogeno -4'-alkyloxybiphenyl-4-carboxylic acids, or that6-hydroxynaphthalene-2-carboxylic acid 2"-methylbutyl ester was replacedwith various optically active 5-halogeno-6-hydroxynaphthalene-2-carboxylacid alkyl esters or optically active 6-hydroxynaphthalene-2-carboxylicacid alkyl esters, in order to prepare various optically active estercompounds. Their phase transition temperatures which are physical valuesare set forth in Table 4.

EXAMPLE 165 Preparation of(s)-6-(2'-methylbutyloxy)-2-naphthyl-4"-octyloxybiphenyl-4'"-carboxylicacid ester

To 30 ml of methylene chloride were added 400 mg of4'-octyloxybiphenyl-4-carboxylic acid, 290 mg of(s)-6-(2'-methylbutyloxy)--2-naphthol, 260 mg ofN,N'-dicyclohexylcarbodiimide and 20 mg of 4-pyrrolidinopyridine, andthe resulting mixture was then allowed to stand at room temperature for20 hours. A secondarily produced N,N'-dicyclohexyl urea was thenfiltered out, and an organic layer was washed with a 5% hydrochloricacid solution, a 5% aqueous sodium hydroxide solution and water in thisorder, followed by drying with anhydrous magnesium sulfate.

After the removal of methylene chloride by distillation, the resultingresidue was then purified by the use of a silica gel columnchromatography utilizing benzene as an eluent. The thus obtained crystalwas recrystallized out of ethanol-ethyl acetate to prepare 280 mg of thedesired6-((s)-2'-methylbutyloxy)--2-naphthyl-4"-octyloxybiphenyl-4'"-carboxylicacid ester in the state of a colorless needle crystal. The yield was42%. A phase transition temperature of the thus prepared compound is setforth in Table 4. Analytical values of elements constituting thiscompound are closely in accord with theoretical values, as follows:

    ______________________________________                                        Theoretical Value (as C.sub.36 H.sub.42 O.sub.4)                                                  Analytical Value                                          ______________________________________                                        C           80.26%      80.07%                                                H            7.86%       7.85%                                                ______________________________________                                    

When measured at a 10° C lower temperature than an SC*-SA transitiontemperature, a value of a spontaneous polarization Ps) was 2 nC/cm².

EXAMPLES 166 TO 170

The same procedure as in Example 165 was repeated with the exceptionthat 4'-octyloxybiphenyl-4-carboxylic acid was replaced with various4'-alkyloxybiphenyl-4-carboxylic acids or optically active4'-alkyloxybiphenyl-4-carboxylic acids, and that(s)-6-(2'-methylbutyloxy)--2-naphthol was replaced with variousoptically active 6-(alkyloxy)--2-naphthols, 6-alkyloxy-2-naphthol or6-alkyl-2-naphthol in order to prepare various optically active estercompounds. Their phase transition temperatures which are physical valuesare set forth in Table 4.

                                      TABLE 4                                     __________________________________________________________________________     Example                                                                            ##STR203##                             Phase transition temperature                                                 (°C.)                      Number                                                                             Wherein A represents      Wherein B represents                                                                     X C   SC* SA  Ch   I                __________________________________________________________________________    152                                                                                 ##STR204##                                                                                              ##STR205##                                                                              H •  93.7                                                                     • 168.2                                                                     • 247.1                                                                     --   •          153  "                         "          Cl                                                                              • 118.7                                                                     (• 97.5)                                                                    • 198.4                                                                     • 215.4                                                                      •          154                                                                                 ##STR206##                                                                                              ##STR207##                                                                              H • 107.5                                                                     • 146.5                                                                     • 200.5                                                                     --   •          155                                                                                 ##STR208##               "          H •  87.0                                                                     • 105.0                                                                     • 185.5                                                                     --   •          156                                                                                 ##STR209##               "          H •  78.5                                                                     • 117.0                                                                     • 183.0                                                                     --   •          157                                                                                 ##STR210##                                                                                              ##STR211##                                                                              H • 105.0                                                                     • 127.3                                                                     • 199.5                                                                     --   •          158                                                                                 ##STR212##               "          H • 109.1                                                                     • 147.8                                                                     • 192.4                                                                     --   •          159                                                                                 ##STR213##               "          H • 111.3                                                                     • 150.5                                                                     • 180.5                                                                     --   •          160                                                                                 ##STR214##                                                                                              ##STR215##                                                                              H •  72.5                                                                     •  76.5                                                                     • 170.8                                                                     --   •          161                                                                                 ##STR216##               "          H •  85.5                                                                     • 107.1                                                                     • 161.5                                                                     --   •          162                                                                                 ##STR217##               "          H •  74.5                                                                     • 127.5                                                                     • 158.5                                                                     --   •          163                                                                                 ##STR218##                                                                                              ##STR219##                                                                              H •  87.5                                                                     •  90.5                                                                     • 169.5                                                                     --   •          164                                                                                 ##STR220##               "          H •  90.3                                                                     • 118.0                                                                     • 186.5                                                                     --   •          165                                                                                 ##STR221##                                                                                              ##STR222##                                                                              H • 147.8                                                                     • 171.0                                                                     • 216.2                                                                     • 230.0                                                                      •          166                                                                                 ##STR223##               OC.sub.10 H.sub.21                                                                       H • 128.1                                                                     • 176.0                                                                     • 183.7                                                                     • 221.8                                                                      •          167                                                                                 ##STR224##                                                                                              ##STR225##                                                                              H • 121.0                                                                     --  • 192.3                                                                     • 197.6                                                                      •          168                                                                                 ##STR226##                                                                                              ##STR227##                                                                              H • 132.0                                                                     • 138.5                                                                     • 192.5                                                                     • 195.5                                                                      •          169                                                                                 ##STR228##               C.sub.6 H.sub.13                                                                         H •  75.0                                                                     •  90.5                                                                     • 110.2                                                                     • 141.0                                                                      •          170  "                         C.sub.7 H.sub.15                                                                         H •  72.7                                                                     •  91.1                                                                     • 112.0                                                                     • 140.0                                                                      •          __________________________________________________________________________

EXAMPLE 171 Preparation of(s)-6-(6'-hexyloxynaphthalene-2'-carbonyloxy)naphthalene-2-carboxylicacid 2"-methylbutyl ester

In 40 ml of methylene chloride were dissolved 530 mg of6-hexyloxynaphthalene-2-carboxylic acid, 500 mg of(s)-6-hydroxynaphthalene-2-carboxylic acid 2'-methylbutyl ester, 400 mgof N,N'-dicyclohexylcarbodiimide and 20 mg of 4-pyrrolidinopyridine, andthe resulting mixture was then allowed to stand at room temperature for5 hours. A secondarily produced N,N'-dicyclohexyl urea was then filteredout, and an organic layer was washed with a 5% hydrochloric acidsolution, a 5% aqueous sodium hydroxide solution and water in thisorder, followed by drying with anhydrous magnesium sulfate.

After the removal of methylene chloride by distillation, the resultingresidue was then purified by the use of a silica gel columnchromatography utilizing benzene as an eluent. The thus obtained crystalwas recrystallized out of ethanol-ethyl acetate ester to prepare 580 mgof the desired(s)-6-(6'-hexyloxynaphthalene-2'-carbonyloxy)naphthalene-2-carboxylicacid 2"-methylbutyl ester in the state of a colorless lamellar crystal.The yield was 58%. A phase transition temperature of the thus preparedcompound is set forth in Table 5. Analytical values of elementsconstituting this compound are closely in accord with theoreticalvalues, as follows:

    ______________________________________                                        Theoretical Value (as C.sub.33 H.sub.36 O.sub.5)                                                  Analytical Value                                          ______________________________________                                        C           77.31%      77.30%                                                H            7.08%       7.10%                                                ______________________________________                                    

EXAMPLES 172 TO 176

The same procedure as in Example 171 was repeated with the exceptionthat 6-hexyloxynaphthalene-2-carboxylic acid was replaced with various6-alkoxynaphthalene-2-carboxylic acid in order to prepare variousoptically active ester compounds. Their phase transition temperatureswhich are physical values are set forth in Table 5.

EXAMPLE 177 Preparation of(s)-6-decyloxy-2-naphthyl-6'-(2"-methylbutyloxy)naphthalene-2'-carboxylicacid ester

To 20 ml of methylene chloride were added 300 mg of(s)-6-(2'-methylbutyloxy)naphthalene-2-carboxylic acid, 350 mg of6-decyloxy-2-naphthol, 240 mg of N,N'-dicyclohexylcarbodiimide and 10 mgof 4-pyrrolidinopyridine, and the resulting mixture was then allowed tostand at room temperature for 3 hours. A secondarily producedN,N'-dicyclohexyl urea was then filtered out, and an organic layer waswashed with a 5% hydrochloric acid solution, a 5% aqueous sodiumhydroxide solution and water in this order, followed by drying withanhydrous magnesium sulfate.

After the removal of methylene chloride by distillation, the resultingresidue was then purified by the use of a silica gel columnchromatography utilizing benzene as an eluent. The thus obtained crystalwas recrystallized out of ethanol-ethyl acetate to prepare 320 mg of thedesired(s)-6-decyloxy-2-naphthyl-6'-(2"-methylbutyloxy)naphthalene-2'-carboxylicacid ester in the state of a colorless needle crystal. The yield was51%. A phase transition temperature of the thus prepared compound is setforth in Table 5. Analytical values of elements constituting thiscompound are closely in accord with theoretical values, as follows:

    ______________________________________                                        Theoretical Value (as C.sub.36 H.sub.44 O.sub.4)                                                  Analytical Value                                          ______________________________________                                        C           79.96%      80.03%                                                H            8.20%       8.15%                                                ______________________________________                                    

EXAMPLE 178

The same procedure as in Example 177 was repeated with the exceptionthat (s)-6-(2'-methylbutyloxy)naphthalene-2-carboxylic acid was replacedwith (s)-6-(4'-methylhexyloxy)naphthalene-2-carboxylic acid in order toprepare an optically active ester compound. Its phase transitiontemperature which is a physical value is set forth in Table 5.

                                      TABLE 5                                     __________________________________________________________________________     Example                                                                             ##STR229##                           Phase transition temperature                                                 (°C.)                       Number                                                                              Wherein A represents    Wherein B represents                                                                     X C    SX  SA  Ch   I                __________________________________________________________________________    171                                                                                  ##STR230##                                                                                            ##STR231##                                                                              H • 133.3                                                                      --  • 152.7                                                                     • 157.4                                                                      •          172                                                                                  ##STR232##             "          H • 82.5                                                                       --  • 152.5                                                                     --   •          173                                                                                  ##STR233##             "          H • 76.9                                                                       (• 63.1)                                                                    • 150.0                                                                     --   •          174                                                                                  ##STR234##             "          H • 91.1                                                                       (• 76.5)                                                                    • 147.8                                                                     --   •          175                                                                                  ##STR235##             "          H • 71.8                                                                       (• 66.4)                                                                    • 144.4                                                                     --   •          176                                                                                  ##STR236##             "          H • 71.1                                                                       •  76.5                                                                     • 141.5                                                                     --   •          177                                                                                  ##STR237##             C.sub.10 H.sub.21                                                                        H • 95.0                                                                       --  --  • 143.3                                                                      •          178                                                                                  ##STR238##             C.sub.10 H.sub.21                                                                        H • 85.7                                                                       • 107.5                                                                     --  • 153.9                                                                      •          __________________________________________________________________________

EXAMPLE 179 Preparation of(R)--6-(trans-4'-butylcyclohexylcarbonyloxy)-2-naphthalenecarboxylicacid 1"-methylheptyl ester

In 50 ml of chloroform were dissolved 1 g oftrans-4-butylcyclohexylcarboxylic acid, 1.7 g of(R)-6-hydroxynapthalene-2-carboxylic acid 1'-methylheptyl ester, 1.2 gof N,N'-dicyclohexylcarbodiimide and 20 mg of 4-pyrrolidinopyridine, andthe resulting mixture was then allowed to stand at room temperature for8 hours. A secondarily produced N,N'-dicyclohexyl urea was then filteredout, and an organic layer was washed with a 2N hydrochloric acidsolution, a 2N aqueous sodium hydroxide solution and water in thisorder.

This material was then purified by the use of a silica gel columnchromatography-utilizing benzene as an eluent in order to prepare 1.2 gof the desired(R)--6-(trans-4'-butylcyclohexylcarbonyloxy)-2-naphthalenecarboxylicacid 1"-methylheptyl ester in a colorless oily state. The yield was 47%.A phase transition temperature of the thus prepared compound is setforth in Table 6. Analytical values of elements constituting thiscompound are closely in accord with theoretical values, as follows:

    ______________________________________                                        Theoretical Value (as C.sub.30 H.sub.42 O.sub.4)                                                  Analytical Value                                          ______________________________________                                        C           77.21%      77.25%                                                H            9.07%       9.10%                                                ______________________________________                                    

EXAMPLE 180

The same procedure as in Example 179 was repeated with the exceptionthat trans-4-butylcyclohexylcarboxylic acid was replaced withtrans-4-nonylcyclohexylcarboxylic acid in order to prepare an opticallyactive ester compound. Its phase transition temperature which is aphysical value is set forth in Table 6.

EXAMPLES 181 TO 184

The same procedure as in Example 179 was repeated with the exceptionthat trans-4-butylcyclohexylcarboxylic acid was replaced with varioustrans-4-alkylcyclohexylcarboxylic acids and that(R)-6-hydroxynaphthalene-2-carboxylic acid 1'-methylheptyl ester wasreplaced with various optically active 6-hydroxynaphthalene-2-carboxylicacid alkyl esters in order to prepare various optically active estercompounds. Their phase transition temperatures which are physical valuesare set forth in Table 6.

                                      TABLE 6                                     __________________________________________________________________________     Example                                                                            ##STR239##                      Phase transition temperature                                                 (°C.)                             Number                                                                             Wherein A represents                                                                     Wherein B represents                                                                             X C   SC*                                                                              SA Ch I                           __________________________________________________________________________    179                                                                                 ##STR240##                                                                               ##STR241##        H <10                                      180                                                                                 ##STR242##                                                                              "                  H <10                                      181                                                                                 ##STR243##                                                                               ##STR244##        H <10                                      182                                                                                 ##STR245##                                                                              "                  H <10                                      183                                                                                 ##STR246##                                                                               ##STR247##        H <10                                      184                                                                                 ##STR248##                                                                               ##STR249##        H <10                                      __________________________________________________________________________

EXAMPLE 185 Preparation of(s)-3-chloro-4-(6'-tetradecyloxy-2'-naphthoyloxy)benzoic acid4"-(2"'-methylbutyloxy)phenyl ester

(i) Preparation of (s)-3-chloro-4-hydroxybenzoicacid-4'-(2"'-methylbutyloxy)phenyl ester:

This compound was prepared from (s)-4-(2'-methylbutyloxy)phenol and4-hydroxy-3-chlorobenzoic acid in accordance with a method described inthe literature, J. Org. Chem. 40, 2998 (1975). A melting point of theproduct was within the range of 165.2° to 166.8° C.

(ii) In 30 ml of methylene chloride were dissolved 500 mg of3-chloro-4-hydroxybenzoic acid-4'-(2"'-methylbutyloxy)phenyl esterobtained in the above process (i), 500 mg of6-tetradecyloxynaphthalene-2-carboxylic acid, 300 mg ofN,N'-dicyclohexylcarbodiimide and 20 mg of 4-pyrrolidinopyridine, andthe resulting mixture was then allowed to stand at room temperature for20 hours. A secondarily produced N,N'-dicyclohexyl urea was thenfiltered out, and an organic layer was washed with a 5% hydrochloricacid solution, a 5% aqueous sodium hydroxide solution and water in thisorder, followed by drying with anhydrous magnesium sulfate.

After the removal of methylene chloride by distillation, the resultingresidue was then purified by the use of a silica gel columnchromatography utilizing benzene as an eluent. The thus obtained crystalwas then recrystallized out of ethanol-ethyl acetate to prepare 600 mgof the desired (s)-3-chloro-4-(6'-tetradecyloxy-2'-naphthoyloxy)benzoicacid 4"-(2"'-methylbutyloxy)phenyl ester in the state of a colorlessneedle crystal. The yield was 60%. A phase transition temperature of thethus prepared compound is set forth in Table 7. Analytical values ofelements constituting this compound are closely in accord withtheoretical values, as follows:

    ______________________________________                                        Theoretical Value (as C.sub.33 H.sub.53 O.sub.6 Cl)                                                Analytical Value                                         ______________________________________                                        C           68.19%       68.25%                                               H            9.19%        9.18%                                               Cl           6.10%        6.05%                                               ______________________________________                                    

When measured at a 10° C lower temperature than an SC*-SA transitiontemperature, a value of a spontaneous polarization (Ps) was 2 nC/cm².

EXAMPLES 186 TO 189

The same procedure as in the process (ii) of Example 185 was repeatedwith the exception that 6-tetradecyloxynaphthalene-2-carboxylic acid wasreplaced with various 6-alkyloxynaphthalene-2-carboxylic acids in orderto prepare various (s)-3-chloro-4-(6 -alkyloxy-2'-naphthoyloxy)benzoicacid 4"-(2"'-methylbutyloxy)phenyl esters. With regard to typical onesof the thus obtained products, their phase transition temperatures areset forth in Table 7.

                                      TABLE 7                                     __________________________________________________________________________     ##STR250##                                                                   Example                                                                            Wherein A                                                                           Wherein B                       Phase transition temperature                                                  (°C.)                       Number                                                                             represents                                                                          represents                   X  C   SC* SA   Ch  I                 __________________________________________________________________________    185  C.sub.14 H.sub.29 O                                                                  ##STR251##                  H  • 85.2                                                                      • 112.9                                                                     • 141.5                                                                      • 164.0                                                                     •           186  C.sub.8 H.sub.17 O                                                                  "                            H  • 100.5                                                                     --  (• 74.3)                                                                     • 186.4                                                                     •           187  C.sub.10 H.sub.21 O                                                                 "                            H  • 94.6                                                                      • 109.8                                                                     • 121.0                                                                      • 176.3                                                                     •           188  C.sub.12 H.sub.25 O                                                                 "                            H  • 88.5                                                                      • 110.3                                                                     • 136.3                                                                      • 169.6                                                                     •           189  C.sub.16 H.sub.33 O                                                                 "                            H  • 92.3                                                                      • 113.4                                                                     • 140.5                                                                      • 153.8                                                                     •           __________________________________________________________________________

EXAMPLE 190 Preparation of (s)-6-octyloxynaphthalene-2-carboxylic acid2'-methylbutyl ester

In 50 ml of toluene, 2 g of 6-octyloxynaphthalene-2-carboxylic acid and5 ml of thionyl chloride were heated at reflux temperature for 5 hours.The used toluene and excessive thionyl chloride were distilled out underreduced pressure, and the resulting residue was then dissolved in 20 mlof toluene and was added to 10 ml of a pyridine solution containing 1 gof (s)-2-methylbutanol, followed by stirring at room temperature for 10hours. The reaction mixture was then washed with a 20% hydrochloric acidsolution, a 10% aqueous sodium hydroxide solution and water in thisorder. An organic layer was then dried with anhydrous magnesium sulfate.After the removal of toluene by distillation, a residual oil was thenpurified by the use of a silica gel column chromatography. The thuspurified oil was dissolved in 5 ml of n-hexane and was then cooled at-20° C. to prepare 1.2 g of the desired(s)-6-octyloxynaphthalene-2-carboxylic acid 2'-methylbutyl ester in thestate of a colorless lamellar crystal. The yield was 49%.

A phase transition temperature of the thus prepared compound is setforth in Table 8. Analytical values of elements constituting thiscompound are closely in accord with theoretical values, as follows:

    ______________________________________                                        Theoretical Value (as C.sub.24 H.sub.34 O.sub.3)                                                  Analytical Value                                          ______________________________________                                        C           77.80%      77.85%                                                H            9.25%       9.19%                                                ______________________________________                                    

EXAMPLE 191 TO 199

The same procedure as in Example 190 was repeated with the exceptionthat 6-octyloxynaphthalene-2-carboxylic acid was replaced with various6-alkyloxynaphthalene-2-carboxylic acids or various6-alkylnaphthalene-2-carboxylic acids, in order to prepare variousoptically active ester compounds. Their phase transition temperatureswhich are physical values are set forth in Table 8.

EXAMPLES 200 TO 225

The same procedure as in Example 190 was repeated with the exceptionthat 6-octyloxynaphthalene-2-carboxylic acid was replaced with various6-alkyloxynaphthalene-2-carboxylic acids, and that (s)-2-methylbutanolwas replaced with various optically active alcohols, in order to preparevarious optically active ester compounds. Their phase transitiontemperatures which are physical values are set forth in Table 8.

EXAMPLE 226 Preparation of (s)-4-methylcaproicacid-2'-(6'-decyloxy)naphthyl ester

To a 15 ml of methylene chloride were added 600 mg of6-decyloxy-2-naphthol, 260 mg of (s)-4-methylcaproic acid, 420 mg ofN,N'-dicyclohexylcarbodiimide and 10 mg of 4-pyrrolidinopyridine, andthe resulting mixture was then allowed to stand at room temperature for2 hours. A secondarily produced N,N'-dicyclohexyl urea was then filteredout, and an organic layer was washed with a 5% hydrochloric acidsolution, a 5% aqueous sodium hydroxide solution and water in thisorder, followed by drying with anhydrous magnesium sulfate.

After the removal of methylene chloride by distillation, the resultingresidue was then purified by the use of a silica gel columnchromatography utilizing benzene as an eluent in order to prepare 600 mgof the desired (s)-4-methylcaproic acid-2'-(6'-decyloxy)naphthyl ester.The yield was 73%. A phase transition temperature of the thus preparedcompound is set forth in Table 8. Analytical values of elementsconstituting this compound are closely in accord with theoreticalvalues, as follows:

    ______________________________________                                        Theoretical Value (as C.sub.27 H.sub.40 O.sub.3)                                                  Analytical Value                                          ______________________________________                                        C           78.59%      78.40%                                                H            9.77%       9.80%                                                ______________________________________                                    

EXAMPLE 227 TO 229

The same procedure as in Example 226 was repeated with the exceptionthat 6-decyloxy-2-naphthol was replaced with various6-alkyloxy-2-naphthols, in order to prepare various optically activeesters. Their phase transition temperatures which are physical valuesare set forth in Table 8.

EXAMPLES 230 TO 233

The same procedure as in Example 226 was repeated with the exceptionthat 6-decyloxy-2-naphthol was replaced with various6-alkyloxy-2-naphthols, and that (s)-4-methylcaproic acid was replacedwith various optically active carboxylic acids, in order to preparevarious optically active ester compounds. Their phase transitiontemperatures which are physical values are set forth in Table 8.

                                      TABLE 8                                     __________________________________________________________________________     ##STR252##                                                                                                    Phase transition                             Example                                                                            Wherein                                                                              Wherein B            temperature (°C.)                     Number                                                                             A represents                                                                         represents         X C    I                                       __________________________________________________________________________    190  C.sub.8 H.sub.17 O                                                                    ##STR253##        H • 15                                                                         •                                 191  C.sub.6 H.sub.13 O                                                                   "                  H • 21                                                                         •                                 192  C.sub.9 H.sub.19 O                                                                   "                  H • 17                                                                         •                                 193  C.sub.10 H.sub.21 O                                                                  "                  H • 13                                                                         •                                 194  C.sub.11 H.sub.23 O                                                                  "                  H • 10                                                                         •                                 195  C.sub.12 H.sub.25 O                                                                  "                  H • 8                                                                          •                                 196  C.sub.14 H.sub.29 O                                                                  "                  H • 12                                                                         •                                 197  C.sub.16 H.sub.33 O                                                                  "                  H • 17                                                                         •                                 198  C.sub.18 H.sub.37 O                                                                  "                  H • 16                                                                         •                                 199  C.sub.8 H.sub.17                                                                     "                  H <0                                           200  C.sub.6 H.sub.13 O                                                                    ##STR254##        H • 21                                                                         •                                 201  C.sub.8 H.sub.17 O                                                                    ##STR255##        H • 17                                                                         •                                 202  C.sub.10 H.sub.21 O                                                                  "                  H • 14                                                                         •                                 203  C.sub.11 H.sub.23 O                                                                  "                  H • 10                                                                         •                                 204  C.sub.12 H.sub.25 O                                                                  "                  H • 14                                                                         •                                 205  C.sub.14 H.sub.29 O                                                                  "                  H • 12                                                                         •                                 206  C.sub.16 H.sub.33 O                                                                  "                  H • 15                                                                         •                                 207  C.sub.18 H.sub.37 O                                                                  "                  H • 18                                                                         •                                 208  C.sub.6 H.sub.13 O                                                                    ##STR256##        H • 19                                                                         •                                 209  C.sub.8 H.sub.17 O                                                                   "                  H • 13                                                                         •                                 210  C.sub.10 H.sub.21 O                                                                  "                  H • 12                                                                         •                                 211  C.sub.14 H.sub.29 O                                                                  "                  H • 12                                                                         •                                 212  C.sub.16 H.sub.33 O                                                                   ##STR257##        H • 14                                                                         •                                 213  C.sub.18 H.sub.37 O                                                                  "                  H • 13                                                                         •                                 214  C.sub.6 H.sub.13 O                                                                    ##STR258##        H • 20                                                                         •                                 215  C.sub.8 H.sub.17 O                                                                   "                  H • 17                                                                         •                                 216  C.sub.10 H.sub.21 O                                                                  "                  H • 14                                                                         •                                 217  C.sub.12 H.sub.25 O                                                                  "                  H • 15                                                                         •                                 218  C.sub.10 H.sub.21 O                                                                   ##STR259##        H • 18                                                                         •                                 219  C.sub.10 H.sub.21 O                                                                   ##STR260##        H <0                                           220  C.sub.8 H.sub.17 O                                                                    ##STR261##        H <0                                           221  C.sub.8 H.sub.17 O                                                                    ##STR262##        H • 12                                                                         •                                 222  C.sub.9 H.sub.19 O                                                                    ##STR263##        H <10                                          223  C.sub.11 H.sub.23 O                                                                   ##STR264##        H <10                                          224  C.sub.10 H.sub.21 O                                                                   ##STR265##        H <10                                          225  C.sub.10 H.sub.21 O                                                                   ##STR266##        H <10                                          226  C.sub.10 H.sub.21 O                                                                   ##STR267##        H • 34.9                                                                       •                                 227  C.sub.8 H.sub.17 O                                                                   "                  H • 31.0                                                                       •                                 228  C.sub.12 H.sub.25 O                                                                  "                  H • 30.3                                                                       •                                 229  C.sub.14 H.sub.29 O                                                                  "                  H • 32.0                                                                       •                                 230  C.sub.8 H.sub.17 O                                                                    ##STR268##        H • 51.5                                                                       •                                 231  C.sub.10 H.sub.21 O                                                                  "                  H • 46.5                                                                       •                                 232  C.sub.8 H.sub.17 O                                                                    ##STR269##        H • 27.5                                                                       •                                 233  C.sub.10 H.sub.21 O                                                                   ##STR270##        H • 26.2                                                                       •                                 __________________________________________________________________________

EXAMPLE 234

A liquid crystal composition was prepared from the following threeliquid crystal compounds of the present invention ##STR271## in amountsof 4 parts, respectively.

The thus prepared liquid crystal composition was indicative of an SC*phase at a temperature up to 47° C., an SA phase within the range of 47°to 95° C., and the state of an isotropic liquid at a higher temperature.Therefore, this composition is desirable as a material for displayelements used in the vicinity of room temperature.

This composition was afterward placed in a cell having a pair ofelectrodes a space between which was 5 μm and which had been subjectedto a rhombic vapor deposition of silica. The liquid crystal cell wasthen put between two light polarizers disposed in the relation ofcrossed Nicols, and an alternating voltage of 10 V having a lowfrequency (1 Hz) was applied to the cell. At this time, a clearswitching phenomenon was observed and a contrast of the cell was verysharp, and in addition, a response speed was fairly high (80 μsec). Inthis case, a value of a spontaneous polarization (Ps) was 42 nC/cm².

EXAMPLE 235

A liquid crystal composition was prepared from the following threeliquid crystal compounds of the present invention ##STR272## in amountsof 2 parts, respectively.

The thus prepared liquid crystal composition was indicative of an SC*phase at a temperature up to 40° C., an SA phase within the range of 40°to 67° C., and the state of an isotropic liquid at a higher temperature.Therefore, this composition is desirable as a material for displayelements used in the vicinity of room temperature.

This composition was afterward placed in a cell having a pair ofelectrodes a space between which was 5 μm and which had been subjectedto a rhombic vapor deposition of silica. The liquid crystal cell wasthen put between two light polarizers disposed in the relation ofcrossed Nicols, and an alternating voltage of 10 V having a lowfrequency (1 Hz) was applied to the cell. At this time, a clearswitching phenomenon was observed and a contrast on the cell was verysharp, and in addition a response speed was fairly high (100 μsec). Inthis case, a value of a spontaneous polarization (Ps) was 38 nC/cm².

EXAMPLE 236

A liquid crystal composition was prepared from a known liquid crystalcompound having the formula ##STR273## (in this compound, a phasetransition temperature was a ##STR274## and a response speed was 1 msec)in an amount of 10 parts and a compound of the present invention havingthe formula ##STR275## in an amount of 1 part.

The thus prepared composition was indicative of the following phasetransition temperature: ##STR276##

Similarly, this composition was placed in the same cell as in Example234 and a response speed was then measured. It was 500 μsec, and thisfact indicates that the conventional compound was remarkably improved inpoint of the response speed.

EXAMPLE 237

Following the same procedure as in Example 236, a composition wasprepared by mixing a compound of the present invention having theformula ##STR277## in an amount of 1 part with a liquid crystal compound(response speed 1 msec) of the present invention having the formula##STR278## in an amount of 10 parts. The thus prepared composition hadthe following phase transition temperature: ##STR279##

Therefore, the composition can work at room temperature. Further, aresponse speed of the composition was 200 μsec which was much higherthan that of the mixture in Example 236.

As is apparent from the foregoing, among the compounds of the presentinvention, even ones which do not show any liquid crystal phase can workat a temperature in the vicinity of room temperature and can thus beconsidered to be useful to obtain liquid crystal compositions having ahigh response speed.

EXAMPLE 238

The compound prepared in Example 9 and known optically active 4-l-decyloxybenzylidene-4'-amino-2"-methylbuthyl cinnamate (DOBAMBC) havingthe chemical structure 1 in Table 1 were each placed in a sample tube,and each sample was allowed to stand in an atmosphere at a temperature60° C. and a humidity of 90% for 40 hours, and before and after thisstanding step, the variation of an SC*-SA transition temperature wasmeasured.

The SC*-SA transition temperature of DOBAMBC dropped as much as 20° C.of from 95° to 75° C., whereas that of the compound prepared in Example9 did not vary at all. This fact indicates that the latter compound isvery stable to the moisture.

EXAMPLE 239

The compound prepared in Example 9 and the known DOBAMBC were eachplaced in a glass tube, and light irradiation was carried out for 30hours by the use of a carbon arc. Before and after the irradiation step,the variation of an SC*-SA transition temperature was measured.

The SC*-SA transition temperature of DOBAMBC dropped as much as 20° C.of from 95° C. to 75° C., whereas that of the compound prepared inExample 9 did not vary at all. This fact indicates that the lattercompound is very stable to the light.

What is claimed is:
 1. Optically active naphthalene derivativesaccording to formula II: ##STR280## wherein R¹ is C₆ -C₁₄ alkoxy and R²is selected from the group consisting of:

    --OCH.sub.2 C*H(OR.sup.3)CH.sub.3

wherein R³ is C₁ -C₄ alkyl.
 2. The naphthalene derivative according toclaim 1, wherein R¹ is C₈ -C₁₂ alkoxy and R³ is ethyl.
 3. Thenaphthalene derivative according to claim 1, wherein R¹ is C₈ -C₁₂alkoxy and R³ is propyl.